Herbicidal substituted 3-aryl-pyrazoles

ABSTRACT

The invention herein relates to certain substituted-arylpyrazole compounds, herbicidal compositions containing same, herbicidal methods of use and processes for preparing said compounds.

FIELD OF THE INVENTION

The field of the invention contemplated herein pertains to herbicidalcompounds generically defined by the above title, to compositionscontaining same and processes for preparing said compounds.

BACKGROUND OF THE INVENTION

Various substituted 3-aryl-pyrazole type compounds are known in theliterature. Such compounds have various utilities, e.g., as chemicalintermediates, pharmaceuticals and herbicides.

Among the substituted 3-aryl-5-(halo) alkyl-pyrazoles in the art arethose having a variety of substituent radicals on the aryl and/orpyrazole moieties of the compound, e.g., alkyl, carboxyl,alkoxycarbonyl, formyl, phenyl and phenyl substituted with variousgroups such as alkyl, halo or nitro groups, etc. For example, compoundsof this type are known wherein the aryl moiety is a substituted orunsubstituted phenyl radical, in which the substituent radicals arealkyl, cycloalkyl, alkaryl, halogen, trifluoromethyl, etc., and thepyrazolyl radical is substituted in various positions on the nitrogen orcarbon atoms with alkyl, halogen, alkoxy, hetero-cycles, S(O)_(n) Rmembers, wherein n is 0-2 and R may be a variety of radicals such asthose substituted on the aryl or pyrazole moieties.

Compounds of the above type having utility as herbicides, typicallyrequire application rates as high as five or ten or more kilograms perhectare to achieve adequate weed control. For example, Japanese patentapplication No. 1-225724 by Miura et al. discloses a number of 3-phenylpyrazole derivatives most of which required a dose of 5 kg/hectare foradequate weed control in both pre-emergent and post emergent tests. Inparticular, 3-phenyl pyrazole derivatives having alkyl or haloalkylsubstitutions in the 4 position of the pyrazole ring were disclosed andexemplified by two compounds having 4-methyl substitutions and in the 5position either --SCH₃ (compound 360) or --SOCH₃ (compound 570). Onlyone of these, compound No. 360, was tested for weed control and a doseof 5 kg/hectare was required for effective post-emergent weed control.At 0.8 Kg/hectare, weed control was ineffective.

Thus, in accordance with the present invention, it has been discoveredthat a novel class of 4-substituted alkyl and haloalkylarylpyrazole-type compounds have uniquely and surprisingly highphytotoxic unit activity against a spectrum of weeds, includingnarrow-leaf and broadleaf weeds yet maintain a high degree of safety ina plurality of crops, especially small grains and/or row crops such aswheat, barley, corn, soybeans, peanuts, etc.

The 1-(halo)alkyl-3-(substituted)aryl-4-(halo)alkyl-5-haloalkylpyrazolesdescribed herein are new.

SUMMARY OF THE INVENTION

This invention relates to herbicidally-active compounds, compositionscontaining these compounds, processes for making them and herbicidalmethods of using the same.

The herbicidal compounds of this invention are characterized by thestructure of Formula I ##STR1## and agriculturally-acceptable salts andhydrates thereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈alkenyl or alkynyl; benzyl; or said R₁ members substituted with halogen,amino, nitro, cyano, hydroxy, alkoxy, alkylthio, ##STR2## R₂ is C₁₋₆haloalkyl; R₃ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, CHO or CH₂ OH;

R₄ members are independently an R₁ member, thioalkyl, polyalkoxyalkyl,carbamyl, halogen, amino, nitro, cyano, hydroxy, C₃₋₁₀ heterocyclecontain O, S(O)_(m) and/or NR₁₈ hetro atoms, C₆₋₁₂ aryl, aralkyl oralkaryl, ##STR3## YR₁₅, or NR₁₆ R₁₇ group; or two R₄ groups may becombined through a saturated and/or unsaturated carbon, --(C═X)--, orhetero O, S(O)_(m) and/or NR₁₈ linkage to form a cyclic ring having upto 9 ring members which may be substituted with an R₁ member, halogen,amino, nitro, cyano, hydroxy, aryl, aralkyl, alkaryl, ##STR4## YR₁₅ orNR₁₆ R₁₇ ; X is O, S(O)_(m), NR₁₉ or CR₂₀ R₂₁ ;

Y is O, S(O)_(m) or NR₂₂ ;

R₈₋₂₂ are hydrogen, C₁₋₈ alkyl, C₃₋₈ cycloalkyl, cycloalkenyl,cycloalkylalkyl, or cycloalkenylalkyl, C₂₋₈ alkenyl or alkynyl, benzyl,or said R₁ members substituted with halogen, amino, nitro, cyano,hydroxy, alkoxy, alkylthio, halogen, amino, nitro, cyano, hydroxy, aryl,aralkyl, alkaryl, carboxyl, alkoxyalkyl, alkylamino, dialkylamino,alkoxy, or carbamyl;

m is 0-2 and

n is 1-5.

A preferred subgenus of the substituted-arylpyrazolyl compounds in thisinvention are those according to Formula II: ##STR5## andagriculturally-acceptable salts and hydrates thereof wherein R₁ is C₁₋₆alkyl;

R₂ is C₁₋₆ haloalkyl;

R₅ and R₆ are independent halogen; and

R₇ is ##STR6##

Particularly preferred compounds of this invention are compoundsaccording to Formula II and agricultuarlly-acceptable salts and hydratesthereof wherein

R₁ is CH₃ ;

R₂ is CF₃ ;

R₃ is CH₃, CH₂ F or CF₂ H;

R₅ is F;

R₆ is Cl; and

R₇ is ##STR7##

Particularly preferred species of this invention include the following:

2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester;

2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid ethyl ester;

2-chloro-5-[4-(difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester; and

2-chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester.

These compounds collectively provide out-standing control of resistantbroadleaf weeds such as pigweed, cocklebur, velvetleaf and hemp sesbaniain various crops such as corn, soybean and nuts and in forestry againsttrees and vines. Other of the compounds of this invention exhibitexcellent herbicidal effect against weeds in other crops such as wheatand barley.

Some of the compounds of the present invention may have more than onepossible stereoisomer and these stereoisomers may differ in herbicidalefficacy. The structures illustrated are intended to include allpossible stereoisomers.

The above compounds may be suitably applied in a variety of applicationmodes, e.g., pre-emergent and/or postemergent, surface applied,pre-plant incorporated, etc.

Another aspect of this invention relates to processes for preparing thecompounds according to Formulae I and II and their precursors,intermediates and/or starting materials. Process I details theconversion of 4-halopyrazoles to 4-alkylpyrazoles and related4-substituted pyrazoles via a pyrazole anion intermediate. The anionicintermediate such as the 4-lithiopyrazole obtained from treatment of a4-bromopyrazole with an alkyllithium reagent is important for thesuccess of this process step. Although anions of pyrazoles are known forthe 3 and 5 positions of the pyrazole ring, anions of the 4 position of5-haloalkylpyrazoles are novel (Heterocycles (1994), 37, 2087-2147).Pyrazoles having a hydrogen substituent in the four position do notprovide 4-lithiopyrazoles on treatment with alkyllithium bases. Thehalogen in the four position was required for this transformation via ahalogen-metal exchange. The anionic intermediate must be treated with asuitable electrophile prior to regiochemical scrambling of the pyrazoleanion in order to obtain 4-substituted pyrazoles as the major product.

Process II describes a cyclocondensation route towards 4-alkylpyrazolesfrom a ketovinylether of Formula C and either hydrazine or analkylhydrazine. Cyclocondensation of allyl substituted diketones withhydrazine to give 4-allyl-5-trifluoromethylpyrazoles is known(Synthesis, 1986, 340), however, routes towards3-aryl-4-alkyl-5-trifluoromethylpyrazoles were previously unknown. Thecyclocondensation described in Process II is a unique method utilizingketovinylethers of Formula C to provide direct access to compounds ofFormula I.

Process III describes transformations of the novel compounds of FormulaI to various derivatives having desired carbon substitutions in the5-position of the phenyl ring. Process IV describes the conversion ofnew compounds of Formula I (where R₃ is CHO) to 4-fluoromethylpyrazolesand 4-difluoromethylpyrazoles. These process aspects will be discussedin more detail below.

Other aspects of this invention relate to herbicidal compositionscontaining the compounds of Formulae I and II and to herbicidal methodsof using those compositions to control undesirable weeds.

It is further within the purview of this invention that thesubstituted-arylpyrazole compounds of Formulae I and II be formulated incompositions containing other herbicidal compounds as co-herbicides,e.g., acetamides, esp., acetanilides, thiocarbamates, ureas,sulfonylureas, sulfonamides, imidazolinones, benzoic acid and itsderivatives, diphenyl ethers, salts of glyphosate, etc.

Other additaments may be included in such herbicidal formulations asdesired and appropriate, e.g, plant disease control agents, such asfungicides, insecticides, nematicides and other pesticides.

As used herein, the terms "alkyl", "alkenyl", alkynyl" when used eitheralone or in compound form, e.g., haloalkyl, haloalkenyl, alkoxy,alkoxyalkyl, etc., are intended to embrace linear or branched-chainmembers. Preferred alkyl members are the lower alkyls having from 1 to 4carbon atoms and preferred alkenyl and alkynyl members are those havingfrom 2 to 4 carbon atoms.

The term "haloalkyl" is intended to mean alkyl radicals substituted withone or more halogen (chloro, bromo, iodo or fluoro) atoms; preferredmembers of this class are those having from 1 to 4 carbon atoms,especially the halomethyl radicals, e.g., trifluoromethyl. Inpolyhaloalkyl members, the halogens can all be the same or mixedhalogens.

Representative, non-limiting alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl members include thefollowing:

Methyl, ethyl, the isomeric propyls, butyls, pentyls, hexyls, heptyls,octyls, nonyls, decyls, etc.; vinyl, allyl, crotyl, methallyl, theisomeric butenyls, pentenyls, hexenyls, heptenyls, octenyls; ethynyl,the isomeric propynyls, butynyls, pentynyls, hexynyls, etc.; the alkoxy,polyalkoxy, alkoxyalkyl and polyalkoxyalkyl analogs of the foregoingalkyl groups, e.g., methoxy, ethoxy, propoxys, butoxys, pentoxys andhexoxys and corresponding polyalkoxys and alkoxyalkyls, e.g.,methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxy-ethoxy,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxymethyl,isopropoxymethyl, butoxymethyl, isobutoxymethyl, tertbutoxymethyl,pentoxymethyl, hexoxymethyl, etc., cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclobutylmethyl,cyclopentylmethyl, etc.; the isomeric cyclopentenes, cyclohexenes andcycloheptenes having mono- or di-unsaturation; representative aryl,aralkyl and alkaryl groups include phenyl, the isomeric tolyls andxylyls, benzyl, naphthyl, etc.

Representative mono-, di- and tri- haloalkyl members include:chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl,iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1,-dichloromethyl,1,1-di-bromomethyl, 1,1-dichloropropyl, 1,2-dibromopropyl,2,3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl,trifluoromethyl, trichloromethyl, etc.

Representative heterocyclic members include: alkylthiodiazolyl;piperidyl; piperidylalkyl; dioxolanylalkyl, thiazolyl; alkylthiazolyl;benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl;furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl;3-cyanothienyl; thienylalkyl; alkyl-substituted thienyl;4,5-polyalkylene-thienyl; piperidinyl; alkylpiperidinyl; pyridyl; di- ortetrahydropyridinyl; alkyltetrahydromorpholyl; alkylmorpholyl;azabicyclononyl; diazabicycloalkanyl, benzoalkylpyrrolidinyl;oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidyl; furyloxazolidinyl,thienyloxazolidinyl, pyridyloxazolidinyl, pyrimidinyloxazolidinyl,benzooxazolidinyl, C₃₋₇ spiro-cycloalkyloxazolidinyl, alkylaminoalkenyl;alkylideneimino; pyrrolidinyl; piperidonyl; perhydroazepinyl;perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl;perhydro-1,4-diazepinyl; quinolinyl, isoquinolinyl; di-, tetra- andperhydroquinolyl- or -isoquinolyl; indolyl and di- and perhydroihdolyland said heterocyclic members substituted with radicals such as definedin Formula I.

By "agriculturally-acceptable salts" of the compounds defined by theabove formulae is meant a salt or salts which readily ionize in aqueousmedia to form a cation or anion of said compounds and the correspondingsalt anion or cation, which salts have no deleterious effect on theherbicidal properties of a given herbicide and which permit formulationof various mixtures, e.g., herbicide-antidote compositions without undueproblems of mixing, suspension, stability, applicator equipment use,packaging, etc.

By "herbicidally-effective" is meant the amount of herbicide required toeffect a meaningful injury or destruction to a significant portion ofaffected undesirable plants or weeds. Although of no hard and fast rule,it is desirable from a commercial viewpoint that 80-85% or more of theweeds be destroyed, although commercially significant suppression ofweed growth can occur at much lower levels, particularly with some verynoxious, herbicide-resistant plants.

DETAILED DESCRIPTION OF THE INVENTION

The compounds according to this invention are suitably prepared by avariety of processes as will be described below. The phenylpyrazoles ofFormula A required for preparation of compounds of Formula I by ProcessI were obtained as previously described in U.S. Pat. No. 5,281,571.Compounds of Formula B were either known in the art or obtained by themethods described in copending U.S. Ser. Nos. 08/277,724 and 08/277,725both filed on Jul. 20, 1994.

Process I

This process describes the preparation of compounds of Formula I fromcompounds of Formula A wherein Z is chlorine, bromine or iodine.##STR8##

In this process description, compounds of Formula I are prepared bytreatment of compounds of Formula A with a suitable base, sequentialaddition of bases or combination of bases followed by treatment with analkylating agent or electrophile. Any inert solvent may be used in thisreaction that does not markedly hinder the reaction from proceeding.Such solvent include, but are not limited to, ethers, cyclic ethers,polyethers, hydrocarbons and aromatic hydrocarbons. The base may bechosen from any number of alkyl lithium, aryllithium, Grignard or otherreagents capable of replacing the halogen Z group of Formula A. Inaddition, base combinations can be used to improve overall conversion oryield. Acidic functionality in the substrate which would otherwise beincompatable with this transformation, such as compounds of Formula Awherein R₄ is a COOH group, can be protected by formation of a salt suchas the lithium, sodium or magnesium carboxylate salts. This can beachieved by addition of excess base or initial formation of thecarboxylate salt with bases such as, but not limited to, sodium hydride,lithium hydride, alkyllithium, aryllithium, Grignard reagents, etc. Theamount of base or combination of bases can range from less than onemolar equivalent to an excess. The intermediate anionic or dianionicspecies obtained after addition of base is treated with an alkylatingagent or suitable electrophile such as methyl iodide, dimethylsulfoxide,dimethylformamide, etc. The amount of alkylating agent or suitableelectrophile can range from less than one molar equivalent to an excess.Reaction temperature is in the range of -150° C. to 100° C., preferably-110° C. to 0° C. The reaction period may be chosen from the range of afew minutes to several weeks depending on the amounts of reagents,reaction temperature, etc. After completion, the reaction mixture istreated with water or aqueous acid and the product is isolated by amethod such a crystallization or solvent extraction. If necessary, theproduct is purified by standard methods.

Process II

This process describes the preparation of compounds of Formula I by amulti-step sequence from alkyl aryl ketones of Formula B. The ketone Bis converted to a vinyl ether C wherein R is an alkyl or aryl groupfollowed by either direct conversion to a compound of Formula I or astepwise formation of pyrazole D followed by alkylation to give acompound of Formula I. ##STR9##

The alkyl aryl ketone B can be converted to a ketal by any of themethods known in the art. This is typically accomplished by addition ofan alcohol or orthoformate to the ketone in the presence of an acid oracid catalyst. A preferred method is treatment of B with trialkylorthoformate in the presence of a strong acid such as, but not limitedto, mineral acid, sulfuric acid, gaseous HCl, etc. Removal of water fromthe reaction mixture will improve the reaction rate and yields ofketals. The ketal is treated with a haloalkyl anhydride in the presenceof pyridine following the method of Hojo, et. al. (Synthesis, 1986, p.1013). A vinyl ether C is obtained which can be treated with hydrazineor a (halo)alkylhydrazine in any suitable solvent to give pyrazole D ora compound of Formula I, respectively. The reaction temperature for thiscyclocondensation step is in the range of -78° C. to 200° C., preferably10°C. to 120° C. The reaction period may be chosen from the range of afew minutes to several weeks depending on the amounts of reagents,reaction temperature, etc. The product is isolated after completion ofthe reaction by filtration and/or concentration of the reaction mixture.If necessary, the product is purified by standard methods such asextraction, crystallization, column chromatography, etc.

In the case of addition of hydrazine to compounds of Formula C, theresultant pyrazole of Formula D may be treated with an alkylating agentto obtain compounds of Formula I. The alkylating agents suitable forthis reaction include methyl iodide, allyl bromide, dimethylsulfate,etc. Preferred solvents are toluene, dimethylsulfoxide, acetonedimethylformamide, dioxane, etc. The reaction may be carried out with orwithout a base. In cases in which a base is employed, alkali metalcarbonates or hydroxides such as sodium carbonate or sodium hydroxidemay be used. Reaction temperature is in the range of -78° C. to 200° C.,preferably 10° C. to 120° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. The product is isolated aftercompletion of the reaction by filtration and/or concentration of thereaction mixture. If necessary, the product is purified by standardmethods such as extraction, crystallization, column chromatrography,etc.

Process III

This process describes the conversion of compounds of Formula II whereinR₇ is a carboxylic acid, to various derivatives of Formula I compoundssuch as benzyl esters, amides, benzyl alcohols, benzyl halides or benzyl(thio)ethers (R₇ is an ester, amide, hydroxyalkyl, haloalkyl,alkoxyalkyl or thioalkyl radical). The compounds of Formula II, whereinR₇ is COOH, require starting materials obtained by either Process I orII. ##STR10##

Compounds of Formula E, wherein R is YR₁₀ or NR₁₁ R₁₂, are obtained fromcompounds of Formula I, wherein R₇ is COOH, by one of the standardmethods for preparation of derivatives of carboxylic acids. This processstep is an esterification or an amide-forming reaction. This may beaccomplished directly from carboxylic acid or its alkali metal salt. Theesterification can be carried out by using an excess of the alcoholcorresponding to the objective ester in the presence of a mineral acid(e.g., sulfuric acid). The amide derivatives can be prepared by treatingthe carboxylic acid with the desired amine either neat or in a suitablesolvent. The esterification or amide-forming reactions can also becarried out in the presence of an inert solvent and a dehydrating agent.

Alternatively, compounds of Formula II, wherein R₇ is COOH, can beconverted to an acid halide or anhydride and treated with an alcohol oramine. Preparation of the acid halide is carried out in the presence ofa halogenating agent such as, but not limited to, thionyl chloride,phosphorus pentachloride, oxalyl chloride, etc, with or without an inertsolvent. Any inert solvent which does not interfere with the reactionmay be employed. A catalytic amount of an amine base such astriethylamine, pyridine or dimethylformamide or the like may be addedfor the purpose of promoting this reaction. The reaction temperature isin the range of -20° C. to the boiling point of the solvent used. Thereaction period ranges from several minutes to 48 hours depending uponthe amounts of reactants used and the reaction temperature. Aftercompletion of the reaction, the excess halogenating reagent andsolvent(s) are removed from the reaction product by evaporation ordistillation. The resultant acid halide may be subjected to an amine oralcohol directly and purified by the usual means.

The acid halide is treated with an alcohol or amine to give a compoundor Formula E. Any inert solvent may be employed and a catalytic amountof an amine base such as triethylamine, pyridine or dimethylformamide orthe like may be added for the purpose of promoting this reaction. Thereaction temperature is in the range of -20° C. to the boiling point ofthe solvent used. The reaction period ranges from several minutes to 48hours depending upon the amounts of reactants used and the reactiontemperature. The product is isolated after completion of the reaction byfiltration and/or concentration of the reaction mixture. If necessary,the product is purified by standard methods such as extraction,crystallization, column chromatography, etc.

Compounds of Formula F can be prepared by reduction of the carboxylicacid group of compounds of Formula I using a reducing agent such asdiborane, borane-tetrahydrofuran, borane complex, lithium aluminumhydride, aluminum hydride, etc. Conversion of the benzyl alcohol to abenzyl halide of Formula G can be carried out with any of a number ofhalogenated reagents such as hydrogen halides or inorganic acid halides,including phosphorus tribromide, thionyl chloride, phosphorusoxychloride, phosphorus pentachloride, hydrogen bromide, hydrogeniodide, etc. Compounds of Formula G can be converted to compounds ofFormula H by displacement of the halogen radical X by a suitablenucleophile. Formation of products of Formula H can be carried out bytreatment of compounds of Formula G with an alkoxide, thioalkoxide,amine, alkyl or aryl anion etc., or an alcohol, mercaptan, amine, etc.in the presence of a base in any suitable solvent. The preferredsolvents are dimethylsulfoxide, acetone dimethylformamide, dioxane, etc.The base may be an organic base (such as a trialkylamine or anotherorganic amine) or an inorganic base (an alkali carbonate such aspotassium carbonate or sodium carbonate). Reaction temperature is in therange of 0° C. to 150° C., preferably 10° to 100° C. The reaction periodmay be chosen from the range of a few minutes to several weeks dependingon the amounts of reagents, reaction temperature, etc. The product isisolated after completion of the reaction by filtration and/orconcentration of the reaction mixture. If necessary, the product ispurified by standard methods such as extraction, crystallization, columnchromatography, etc.

Process IV

This section describes a process for the preparation of compounds ofFormulae J, K and L from compounds of Formula I wherein the R₃ radicalis a CHO group. The compounds of Formula I wherein R₃ is a CHO group areobtained by Process I. ##STR11##

In this process, compounds of Formula J are prepared by fluorination ofthe aldehyde group of compounds of Formula I with a suitablefluorinating agent. Any solvent may be employed which does not interferwith the course of the reaction. Fluorinating reagents include, but arenot limited to, diethylaminosulfur trifluoride (DAST),dialkylaminosulfur trifluorides, SF₄, HF, SeF₄, PhSF₃, MoF₆, etc.Compounds of Formula K can be prepared by reduction of the aldehydegroup of compounds of Formula I (R₃ is CHO) using a reducing agent suchas diborane, borane-tetrahydrofuran, borane complex, lithium aluminumhydride, aluminum hydride, etc. Compounds of Formula K are prepared byfluorination of compounds of Formula J with a suitable fluorinatingagent. Fluorinating reagents include, but are not limited to,diethylaminosulfur trifluoride (DAST), dialkylaminosulfur trifluorides,SF₄, HF, SeF₄, PhSF₃, MoF₆, etc. Any of the products J, K or L areisolated after completion of the reaction by filtration and/orconcentration of the reaction mixture. If necessary, the product ispurified by standard methods such as extraction, crystallization, columnchromatography, etc.

Further derivatives of compounds obtained by the above Processes I-IVcan be prepared by any of the processes or methods outlined in U.S. Pat.No. 5,281,571 which is incorporated by reference.

The following Examples 1-15 describe specific working embodiments forthe preparation of representative compounds according to this invention.

Examples 1 through 3 describe specific working embodiments of Process I.

EXAMPLE 1 Preparation of3-(2,5-Difluorophenyl)-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazole

A solution of 10 g of4-bromo-3-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 250 mL anhydrous THF was cooled to -78° C. and stirred with anoverhead stirrer. The cold solution was treated with 12 mL of 2.5Mn-butyllithium in hexanes never allowing the temperature to exceed -70°C. After stirring for 5 minutes, 1.9 mL of methyl iodide was addedquickly. The cooling bath was removed and the solution allowed to warmto room temperature. The solution was diluted with diethyl ether and thecombined organic extracts were washed twice with brine, dried overanhydrous magnesium sulfate and concd in vacuo. Chromatographicpurification (silica, 5% ethyl acetate in hexanes) gave 5.8 g (72.4%) of3-(2,5-difluorophenyl)-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazole asan oil; 1HNMR (CDCl3) δ 2.0 (quintet, 3H, J=2.1 Hz), 3.9 (d, 3H, J=1.2Hz), 6.9-7.1 (m, 3H). Anal. Calcd for C13H9F5N2: C, 52.18; H, 3.28; N,10.14. Found: C, 52.20; H, 3.30; N, 10.11.

EXAMPLE 2 Preparation of2-Chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid

A solution of 30 g of5-[4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-chloro-4-fluorobenzoicacid in 800 mL of anhydrous THF was stirred with a mechanical stirrerand treated with 3.36 g of 80% NaH. The stirred mixture was kept under anitrogen atmosphere and heated to 60° C. for one hour. After formationof the sodium carboxylate salt, the mixture was cooled to -110° C. and32.3 mL of 2.5M n-butyllithium in hexanes was added never allowing thetemperature to exceed -100° C. The reaction was stirred at -110° C. forten minutes, subsequently treated with 9.3 mL of methyl iodide andallowed to warm to room temperature. The mixture was quenched with 3NHCl and the volatiles removed. A precipitate formed which was collectedand recrystallized from ethanol/water to give 24.5 g of a white solid:mp 155.0° C.; ¹ HNMR (CDCl₃) δ 2.06 (m, 3H), 4.01 (s, 3H), 7.27 (d, 1H,J=9.6 Hz), 8.17 (d, 1H, J=7.6 Hz). Anal. Calcd for C₁₃ H₉ O₂ Cl₁ N₂ F₄ :C, 46.38; H, 2.69; N, 8.32. Found: C, 46.46; H, 2.65; N, 8.33.

EXAMPLE 3 Preparation of2-Chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-1-3-yl]benzoicacid

To a mechanically stirred solution of 10 g of5-[4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-chloro-4-fluorobenzoicacid in 400 ml of anhydrous tetrahydrofuran under a nitrogen atmospherewas added 1.0 g of 95% sodium hydride. After the foaming subsided, thereaction was stirred and heated to 60° C. for one hour to ensurecomplete anion formation of the acid. The reaction was cooled to -110°C. with vigorous stirring and a 10.8 mL of 2.5M n-butyl lithium inhexanes was added maintaining the temperature below -100° C. As soon asthe addition of n-butyl lithium was completed, 10 mL of dimethylformamide was added and the solution was allowed to warm to -20° C. Thereaction was then quenched with 3N HCl, and most of the volatiles wereremoved from the reaction mixture. The precipitate was filtered andrecrystalized from carbon tetrachloride to give 3.0 g of2-chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid: mp 163° C.; ¹ HNMR (CDCl₃) ppm: 9.82 (s, 1H), 7.89 (d, 1H, J=7.6),7.07 (d, 1H, J=9.2), 3.39 (s, 3H). ¹⁹ FNMR (CDCl₃) ppm: -57.78, -107.41.

Examples 4 through 7 describe specific working embodiments of ProcessII.

EXAMPLE 4 Preparation of 1-Chloro-4-(1,1-diethoxypropyl)benzene

A solution of 15.0 g of p-chloropropiophenone and 7.8 mL of dry EtOH wastreated with 22.0 mL of triethyl orthoformate. Gaseous HCl was bubbledthrough the solution until saturation and the reaction mixture heated toreflux overnight. An additional 14.8 mL. Of triethyl orthoformate wasadded and the reaction mixture allowed to cool to room temperature. Thecooled mixture was washed with 10% Na₂ CO₃, extracted with diethyl etherand concd in vacuo to afford 19.0 g (88%) of a crude orange/yellow oil.The oil was distilled and a fraction collected (75°-96° C., 100 mtorr)which contained 13.4 g of 1-chloro-4-(1,1-diethoxypropyl)benzene: μ(23,D) 1.5612; ¹ HNMR (CDCl₃) δ 0.56 (t, 3H, 7.5 Hz), 1.19 (t, 6H, 7.0Hz), 1.89 (q, 2H, 7.5 Hz), 3.36 (m, 4H), 7.28 (d, 2H, 8.5 Hz), 7.42 (d,2H, 8.5 Hz). Anal. Calcd for C₁₃ H₁₉ O₂ Cl: C, 64.32; H, 7.89. Found: C,64.09; H, 7.81.

EXAMPLE 5 Preparation of4-(4-Chlorophenyl)-4-ethoxy-1,1,1-trifluoro-3-methyl-3-buten-2-one.

A solution of 2.0 g of 1-chloro-4-(1,1-diethoxypropyl)benzene and 2.5 mLof CH₂ Cl₂ was treated with 1.45 mL of pyridine. The solution was cooledto 0° C. and treated with 5.5 mL of (CF₃ CO)₂ O in 2.5 mL of CH₂ Cl₂.After heating overnight at reflux, the reaction mixture was cooled,diluted with CH₂ Cl₂ and 12 mL of ice cold water was added. The organiclayer was seperated and washed with 20 mL of 1N HCl, followed by awashing with 20 mL of 10% Na₂ CO₃ and two washing with 20 mL of water.The organic layer was dried over Na₂ SO₄ and concd in vacuo to yield1.69 g of a dark brown oil. Chromatographic purification (silica, 10%ethyl acetate in hexanes) yielded 1.0 g of a yellow oil. Bulb to bulbdistillation gave 0.45 g of a very pure light yellow oil: μ(23,D)1.5137; major geometric isomer: ¹ HNMR (CDCl₃) δ 1.22 (t, 3H, 7.0 Hz),1.70 (s, 3H), 3.64 (q, 2H, 7.0 Hz), 7.30 (d, 2H, 8.3 Hz), 7.46 (d, 2H,8.4 Hz). ¹⁹ FNMR (CDCl₃) δ -74.68 (CF₃). Anal. Calcd for C₁₃ H₁₂ O₂ F₃Cl: C, 53.35; H, 4.13. Found: C, 53.44; H, 4.10.

EXAMPLE 6 Preparation of5-(4-Chlorophenyl)-4-methyl-3-(trifluoromethyl)-1H-pyrazole

A solution of 5.5 g of4-(4-chlorophenyl)-4-ethoxy-1,1,1-trifluoro-3-methyl-3-buten-2-one in 20mL of MeOH was slowly treated with 0.70 mL of NH₂ NH₂ and allowed tostir for two hours. Water was added to the reaction mixture and aprecipitate formed. The solid was collected by filtration and washedwith hexanes to yield 3.87 g of5-(4-chlorophenyl)-4-methyl-3-(trifluoromethyl)-1H-pyrazole as a whitepowdery product: mp 139.0° C.; ¹ HNMR (CDCl₃) δ 2.09 (s, 3H), 7.39 (m,2H), 7.45 (m, 2H, 8.5 Hz), 11.75 (bs, 1H). ¹⁹ FNMR (CDCl₃) δ -62.34°(3F). Anal. Calcd for C₁₁ H₈ N₂ F₃ Cl: C, 50.69; H, 3,09; N, 10.57.Found: C, 50.68; H, 3.05; N, 10.81.

EXAMPLE 7 Preparation of3-(4-chlorophenyl)-1,4-dimethyl-5-(trifluoromethyl)pyrazole

To a solution of 3.7 g of5-(4-chlorophenyl)-4-methyl-3-(trifluoromethyl)-1H-pyrazole in 40 mL ofacetone was added 5.9 g of potassium carbonate and 1.8 mL of methyliodide. The mixture was allowed stir overnight at room temperature,filtered and concd in vacuo to give a white solid. This mixture of twoisomeric pyrazoles was purified by chromatography on silica (5% ethylacetate in hexanes) to give 1.8 g (high R_(f)) of3-(4-chlorophenyl)-1,4-dimethyl-5-(trifluoromethyl)pyrazole and 2.15 g(low R_(f)) of5-(4-chlorophenyl)-1,4-dimethyl-3-(trifluoromethyl)pyrazole. The lowR_(f) material was distilled bulb to bulb (0.1 torr) to give a white,crystalline solid: mp 52°-54° C.; ¹ HNMR (CDCl₃) δ 2.06 (q, 3H, J=1.0Hz), 3.77 (s, 3H), 7.26 (d, 2H, J=8.5 Hz), 7.50 (d, 2H, J=8.4 Hz); ¹⁹FNMR (CDCl₃) δ-61.6 (3F). Anal. Calcd for C₁₂ H₁₀ N₂ F₃ Cl₁ : C, 52.47;H, 3.677N, 10.20. Found: C, 52.51; H, 3.70; N, 10.18.

The chromatographically less retained component (high R_(f)) wasrecrystallized from hexanes to give3-(4-chlorophenyl)-1,4-dimethyl-5-(trifluoromethyl)pyrazole as a white,crystalline solid; mp 87°-88.5° C.; ¹ HNMR (CDCl₃) δ 2.25 (q, 3H, J=1.9Hz), 3.99 (s, 3H), 7.39 (d, 2H, J=8.4 Hz), 7.50 (d, 2H, J=8.5 Hz); ¹⁹FNMR (CDCl₃) δ -58.4 (3F). Anal. Calcd for C₁₂ H₁₀ N₂ F₃ Cl₁ : C, 52.47;H, 3.67; N, 10.20. Found: C, 52.48; H, 3.71; N, 10.16.

Examples 8 through 12 describe specific working embodiments of ProcessIII.

EXAMPLE 8 Preparation of2-Chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]4-fluorobenzoicacid, 1-methylethyl ester

To a solution of 18 g of2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid. (Ex. 2) in 400 mL of CH₂ Cl₂ was added 10 g of oxalyl chloride anda few drops of DMF. After 20 minutes at room temperature, the reactionwas heated to reflux for 2 hr and subsequently concd in vacuo. Theresultant solid was dissolved in excess 2-propanol and heated overnightat reflux. The reaction mixture was concd, dissolved in ether, washedwith 10% aq. NaOH and saturated brine and concd to give a solid.Recrystallization from cold hexanes gave 14 g of2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester: mp 72° C.; ¹ HNMR (CDCl₃) δ 1.36 (d, 6H, 6.4Hz), 2.09 (quintet, 3H, 2.0 Hz), 5.25 (heptet, 1H, 6.0 Hz), 7.27 (d, 1H,9.2 Hz), 7.94 (d, 1H, 7.6 Hz). Anal. Calcd for C₁₆ H₁₅ O₂ N₂ F₄ Cl: C,50.74; H, 3.99; N, 7.40. Found: C, 50.85; H, 4.02; N, 7.41.

EXAMPLE 9 Preparation of2-Chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanol

A solution of 1.5 g of2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid (Ex. 2) in 30 mL of anhydrous THF was treated with 10 mL of 1.0Mborane-THF solution and heated to reflux for 24 hr. The mixture wasallowed to cool and added to ice water. A precipitate formed which wascollected by filtration, washed with cold water and dried to give 1.3 gof2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanolas a white solid: mp 58° C.; ¹ HNMR (CDCl₃) δ 2.09 (q, 3H), 4.00 (s,3H), 4.75 (s, 2H), 7.20 (d, 1H), 7.57 (d, 1H).

EXAMPLE 10 Preparation of3-[5-(Bromomethyl)-4-chloro-2-fluorophenyl]-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazole

To a solution of 7.0 g of2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanolin 200 mL of diethyl ether was added 30 mL of phosphorus tribromide andthe mixture allowed to stir overnight. The reaction mixture was pouredinto ice water, the ether removed by concd in vacuo and the resultantsolid collected by filtration. The solid was washed with water and airdried to give a quantitative yield of3-[5-(bromomethyl)-4-chloro-2-fluorophenyl]-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazole:¹ HNMR (CDCl₃) δ 2.17 (t. 3H, 2.0 Hz), 4.07 (s, 3H), 4.64 (s, 2H), 7.30(d, 1H, 9.5 Hz), 7.62 (d, 1H, 7.5 Hz); ¹⁹ FNMR (CDCl₃) δ -58.5 (s, 3F),-111.6 (s, 1F).

EXAMPLE 11 Preparation of3-[(4-Chloro-2-fluoro-5-(methoxymethyl)phenyl]-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazole

A solution of 0.5 g of3-[5-(bromomethyl)-4-chloro-2-fluorophenyl]-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazolein 100 mL of methanol was treated with 0.5 g of potassium carbonate andheated to reflux for five days. The mixture was diluted withmethanol-water and the resultant precipitate collected by filtration.The solid was washed with water and air dried to afford 0.30 g of3-[(4-chloro-2-fluoro-5-(methoxymethyl)phenyl]-1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazoleas a white powder: mp 59° C.; ¹ HNMR (CDCl₃) δ 2.09 (t, 3H, 2.0 Hz),3.44 (s, 3H), 4.00 (s, 3H), 4.53 (s, 2H), 7.20 (d, 1H, 9.6 Hz), 7.55 (d,1H, 8.0 Hz).

EXAMPLE 12 Preparation of2-Chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester

To a slurry of 2.5 g of2-chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid (Ex. 3) in 50 ml of methylene chloride was added 10 mL of oxalylchloride followed by catalytic DMF. The solution was stirred for onehour and concd in vacuo. The resultant residue was diluted in 2-propanoland heated to 50° C. for one hour. The reaction was poured onto waterand extracted into diethyl ether. The combined organic extracts werewashed with brine and 2.5N sodium hydroxide solution, dried and concd togive a material which contained the desired product and a bi-product.Chromatographic purification (silica, 10% ethyl acetate in hexanes)afforded 1.0 g of2-chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester in a 36% yield: mp 90° C.; ¹ HNMR (CDCl₃) δ10.04 (s, 1H), 7.9 (d, 1H, J=7.6), 7.25 (d, 1H, J=9.2), 5.23 (m, 1H),4.11 (s, 3H), 1.35 (d, 6H, J=6.0).

Examples 13 through 15 describe specific working embodiments of ProcessIV.

EXAMPLE 13

Preparation of2-Chloro-5-[4-(difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester

To a solution of 1.5 g of2-chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester in 50 mL methylene chloride was added 7 mL ofdiethyl aminosulfurtrifluoride and the solution stirred overnight atroom temperature. The reaction was poured onto ice water and the organiclayer was washed with brine, dried over anhydrous magnesium sulfate,filtered and concd in vacuo to give 1.0 g of2-chloro-5-[4-(difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester as a yellow solid: mp 57° C.; ¹ HNMR (CDCl₃) δ8.06 (d, 1H, J=7.7), 7.36 (d, 1H, J=9.5), 6.75 (t, 1H, J=55.1), 5.32 (m,1H, J=6.3), 4.16 (s, 3H), 1.42 (d, 6H, J=6.6). ¹⁹ FNMR (CDCl₃) δ -58.56,-108.01, -109.53. Anal. Calcd for C₁₆ H₁₃ Cl₁ F₆ N₂ O₂ : C, 46.34; H,3.16; N, 6.75. Found: C, 46.08; H, 3.25; N, 6.79.

EXAMPLE 14 Preparation of2-Chloro-4-fluoro-5-[4-(hydroxymethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester

To a solution of 0.5 g of2-chloro-4-fluoro-5-[4-formyl-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester in 50 ml of anhydrous tetrahydrofuran wasadded 4 mL of 1M borane in THF solution. The reaction was stirredovernight and then poured onto water, extracted into diethyl ether,dried over anhydrous magnesium sulfate and concd in vacuo to give 0.5 gof2-chloro-4-fluoro-5-[4-(hydroxymethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester as a clear oil: ¹ HNMR (CDCl₃) δ 8.10 (d, 1HJ=7.7,), 7.36 (d, 1H, J=9.6), 5.29 (m, 1H), 4.62 (s, 2H), 4.10 (s, 3H),1.42 (d, 6H, J=6.6); ¹⁹ FNMR (CDCl₃) ppm: -58.82, -109.09.

EXAMPLE 15 Preparation of2-Chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester

To a solution of 0.5 g2-chloro-4-fluoro-5-[4-(hydroxymethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester in 50 ml methylene chloride was added 5 mL ofdiethyl aminosulfurtrifluoride and the solution stirred overnight atroom temperature. The reaction mixture was poured onto ice water and theorganic layer washed with brine, dried over anhydrous magnesium sulfate,filtered and the concd in vacuo to give2-chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester as a tan solid: mp 74° C.; ¹ HNMR (CDCl₃) δ8.02 (d, 1H, J=8.0), 7.30 (d, 1H, J=9.6), 5.29 (d, 2H, J=48.0), 5.26 (m,1H, J=6.0), 4.09 (s, 3H), 1.37 (d, 6H, J=6.4).

Table 1 shows examples of compounds prepared according to ProcessesI-IV. Examples 1 through 15 are described above. Example 16 was preparedby the four step procedure outlined in Process II (Examples 4-7) exceptthat the starting material for the first step was1-(4-chloro-2-fluoro-5-methylphenyl)-1-propanone. Examples 17-32 and41-58 were prepared from Example 2 by methods described in Process III.Example 33 was prepared by Process I from4-bromo-3-(4-chloro-2-fluoro-5-methylphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole.Example 34 was prepared in an analogous manner to Example 1 except thatdimethylformamide was used in place of methyl iodide to quench theintermediate anion. Examples 35 through 40 were prepared from Example 1by methods previously described in U.S. Pat. No. 5,281,571.

                                      TABLE 1                                     __________________________________________________________________________    3-SUBSTITUTED PHENYLPYRAZOLES                                                  ##STR12##                                                                    Cpd.sup.a                   Physical                                          No. R.sub.3                                                                           R.sub.5                                                                          R.sub.6                                                                          R.sub.7       Data.sup.b                                                                          Process                                     __________________________________________________________________________     1  CH.sub.3                                                                          F  H  F             clear oil                                                                           I                                            2  CH.sub.3                                                                          F  Cl COOH          155° C.                                                                      I                                            3  CHO F  Cl COOH          163° C.                                                                      I                                            7  CH.sub.3                                                                          H  Cl H             87-88.5° C.                                                                  II                                           8  CH.sub.3                                                                          F  Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                 72° C.                                                                       III                                          9  CH.sub.3                                                                          F  Cl CH.sub.2 OH   58° C.                                                                       III                                         10  CH.sub.3                                                                          F  Cl CH.sub.2 Br   .sup.c                                                                              III                                         11  CH.sub.3                                                                          F  Cl CH.sub.2 OCH.sub.3                                                                          59° C.                                                                       III                                         12  CHO F  Cl COOCHMe.sub.2 90° C.                                                                       IV                                          13  CHF.sub.2                                                                         F  Cl COOCHMe.sub.2 57° C.                                                                       IV                                          14  CH.sub.2 OH                                                                       F  Cl COOCHMe.sub.2 oil   IV                                          15  CH.sub.2 F                                                                        F  Cl COOCHMe.sub.2 74° C.                                                                       IV                                          16  CH.sub.3                                                                          OH Cl CH.sub.3      109.5-                                                                              II                                                                      110.5° C.                                  17  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CO.sub.2 Et                                                               55° C.                                                                       III                                         18  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.3                                                                           62° C.                                                                       III                                         19  CH.sub.3                                                                          F  Cl CO.sub.2 n-propyl                                                                           60° C.                                                                       III                                         20  CH.sub.3                                                                          F  Cl CO.sub.2 CHMeCO.sub.2 Et                                                                    clear oil                                                                           III                                         21  CH.sub.3                                                                          F  Cl CONH.sub.2    135° C.                                                                      III                                         22  CH.sub.3                                                                          F  Cl CONH(CHMe.sub.2)                                                                            139° C.                                                                      III                                         23  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CO.sub.2 CHMe.sub.2                                                       69° C.                                                                       III                                         24  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CH2CH.sub.2 CO.sub.2 Et                                                   50° C.                                                                       III                                         25  CH.sub.3                                                                          F  Cl CO.sub.2 (3-tetra-                                                                          76° C.                                                                       III                                                       hydrofuranyl)                                                   26  CH.sub.3                                                                          F  Cl CO.sub.2 Et   60° C.                                                                       III                                         27  CH.sub.3                                                                          F  Cl CH.sub.2 SCH.sub.3                                                                          white II                                                                      solid                                             28  CH.sub.3                                                                          F  Cl CH.sub.2 SO.sub.2 CH.sub.3                                                                  white III                                                                     solid                                             29  CH.sub.3                                                                          F  Cl CH.sub.2 SCHMe.sub.2                                                                        white III                                                                     solid                                             30  CH.sub.3                                                                          F  Cl CH.sub.2 SH   brown III                                                                     solid                                             31  CH.sub.3                                                                          F  Cl CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3                                                        yellow                                                                              III                                                                     oil                                               32  CH.sub.3                                                                          F  Cl CH.sub.2 SCH.sub.2 CHMe.sub.2                                                               yellow                                                                              III                                                                     oil                                               33  CH.sub.3                                                                          F  Cl CH.sub.3      67-68° C.                                                                    I                                           34  CHO F  H  F             clear oil                                                                           I                                           35  CH.sub.3                                                                          F  NO.sub.2                                                                         F             65-67° C.                                                                    .sup.d                                      36  CH.sub.3                                                                          F  NO.sub.2                                                                         OCH.sub.3     138° C.                                                                      .sup.d                                      37  CH.sub.3                                                                          F  Cl OCH.sub.3     89° C.                                                                       .sup.d                                      38  CH.sub.3                                                                          F  Cl OCH.sub.2 CO.sub.2 CHMe.sub.2                                                               89° C.                                                                       .sup.d                                      39  CH.sub.3                                                                          F  Cl OCH.sub.2 CCH 109° C.                                                                      .sup.d                                      40  CH.sub.3                                                                          F  Cl OH            115° C.                                                                      .sup.d                                      41  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 Ph                                                                        .sup.c                                                                              III                                         42  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CCH                                                                       .sup.c                                                                              III                                         43  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 COPh                                                                      .sup.c                                                                              III                                         44  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 C(OMe)CHCO.sub.2 Et                                                       .sup.c                                                                              III                                         45  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CHMe.sub.2                                                                .sup.c                                                                              III                                         46  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CHEt.sub.2                                                                .sup.c                                                                              III                                         47  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 (2-morpho-                                                                .sup.c                                                                              III                                                       linyl)                                                          48  CH.sub.3                                                                          F  Cl CO.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                          .sup.c                                                                              III                                         49  CH.sub.3                                                                          F  Cl CO.sub.2 (CH.sub.2).sub.11 CH.sub.3                                                         .sup.c                                                                              III                                         50  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 SCN                                                                       .sup.c                                                                              III                                         51  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CH.sub.2 CHMe.sub.2                                                       .sup.c                                                                              III                                         52  CH.sub.3                                                                          F  Cl CO.sub.2 CHMeCH.sub.2 OMe                                                                   .sup.c                                                                              III                                         53  CH.sub.3                                                                          F  Cl CO.sub.2 (CH.sub.2).sub.3 COCH.sub.3                                                        .sup.c                                                                              III                                         54  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 CHCH.sub.2                                                                .sup.c                                                                              III                                         55  CH.sub.3                                                                          F  Cl CO.sub.2 (CH.sub.2).sub.2 CHMe.sub.2                                                        .sup.c                                                                              III                                         56  CH.sub.3                                                                          F  Cl CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                         .sup.c                                                                              III                                         57  CH.sub.3                                                                          F  Cl CO.sub.2 CH.sub.2 (2-furanyl)                                                               .sup.c                                                                              III                                         58  CH.sub.3                                                                          F  Cl CO.sub.2 CH(CH.sub.3)Et                                                                     .sup.c                                                                              III                                         __________________________________________________________________________     .sup.a Compound numbers correspond to example numbers.                        .sup.b Physical Data include melting point and physical appearance.           .sup.c No physical data were obtained.                                        .sup.d Prepared by methods in U.S. Pat. No. 5,281,571.                   

Pre-Emergence Herbicide Tests

As noted above, the compounds of this invention have been found to besurprisingly effective as herbicides.

The tests for pre-emergence herbicide activity were conducted accordingto the following methods:

Topsoil was placed in an aluminum pan and compacted to a depth of 1.3 to1.6 cm from the top of the pan. On the top of the soil was placed apredetermined number of seeds of each of several monocotyledonous anddicotyledonous annual plant species and/or vegetative propagules ofvarious perennial plant species. The pan was then level filled with acover layer of topsoil to which was added a known amount of activeingredient either prior to or after application of the cover layer. Theactive ingredient was dissolved or suspended in an organic solvent,e.g., acetone, or water as carrier for application to the cover layer.The pans were moved to a greenhouse bench where they were thereafterwatered from below as needed to give adequate moisture for germinationand growth. In some cases, an initial overhead irrigation of 1/4 inch ofwater was applied immediately after treatment.

Approximately 14 days after seeding and treating, the pans were observedand the results (% inhibition) were recorded.

The tables below summarize the results of the pre-emergence herbicidalactivity tests of compounds of this invention tested with warm seasonplants (Tables 2a-2d) and cool season plants (Tables 3a and 3b). Tablesubdivisions a through d represent different spectra of plants tested.The herbicidal rating shown in these tables is the percent inhibition ofeach plant species. The plant species usually regarded as weeds areidentified in the tables by single letter headings and crop speciesidentified by two letter headings both headings being above the columnsin accordance with the following legend:

Weed Species

A=Yellow Foxtail

B=Yellow Nutsedge

C=Barnyardgrass

D=Velvetleaf

E=Morning Glory

F=Cocklebur

G=Blackgrass

H=Common Chickweed

I=Bedstraw Catchweed

J=Broadleaf Signalgrass

K=Wild Proso Millet

L=Seedling Johnsongrass

M=Shattercane

N=Prickly Sida

O=Green Foxtail

P=Giant Foxtail

Q=Sicklepod

R=Black Nightshade

S=Hemp Sesbania

T=Wild Oats

U=Downy Brome

V=Birdseye Speedwell

Crop Species

AA=Rice

BB=Corn

CC=Soybean

DD=Wheat

EE=Rape

Where noted in the tables below, the symbol "ND" indicates that thespecies was planted, but no data obtained for one reason or another.

                                      TABLE 2a                                    __________________________________________________________________________    PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd                                                                              Rate                                                                       No.                                                                              lb/A                                                                              A   B  C  D   E  F  AA BB CC                                           __________________________________________________________________________    1  4.5 35  45 50 65  35 0  0  10 0                                               0.893                                                                             0   0  0  0   0  0  25 0  0                                            34 4.5 20  20 0  75  0  0  0  0  0                                               0.893                                                                             0   0  0  15  0  0  0  0  0                                               0.1785                                                                            0   0  0  0   0  0  0  0  0                                            35 4.5 80  30 95 100 85 90 0  55 55                                              0.893                                                                             35  0  25 100 85 55 25 20 40                                              0.1785                                                                            0   0  0  98  80 60 0  5  0                                               0.893                                                                             35  40 0  98  80 35 0  5  25                                              0.1785                                                                            0   0  0  70  15 25 30 0  0                                               0.0357                                                                            0   0  0  0   0  0  0  0  0                                            36 0.893                                                                             100 0  100                                                                              100 90 85 65 90 10                                              0.1785                                                                            98  0  90 98  60 0  0  55 0                                               0.0357                                                                            15  0  20 20  10 20 0  10 0                                               0.0071                                                                            0   0  0  20  0  0  0  0  0                                            37 0.893                                                                             100 45 100                                                                              100 100                                                                              98 100                                                                              100                                                                              100                                             0.1785                                                                            100 50 100                                                                              100 90 80 85 85 50                                              0.0357                                                                            95  35 100                                                                              100 98 75 0  50 50                                              0.0071                                                                            55  0  80 98  80 100                                                                              25 25 20                                           38 0.893                                                                             65  85 70 100 100                                                                              90 40 40 70                                              0.1785                                                                            25  0  35 98  95 85 0  0  15                                              0.0357                                                                            0   20 15 80  75 65 0  0  5                                               0.0071                                                                            0   0  0  100 20 ND 0  0  0                                            39 0.893                                                                             100 65 100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100                                             0.1785                                                                            100 55 100                                                                              100 100                                                                              95 85 95 95                                              0.0357                                                                            100 25 100                                                                              100 85 80 70 80 100                                             0.0071                                                                            95  70 80 100 70 50 65 10 0                                            40 4.5 100 0  100                                                                              100 100                                                                              100                                                                              65 85 20                                              0.893                                                                             80  70 35 60  50 45 0  5  20                                              0.1785                                                                            0   0  0  0   0  0  0  0  0                                               0.0357                                                                            0   0  0  0   0  0  0  0  0                                            __________________________________________________________________________

                  TABLE 2b                                                        ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd  Rate                                                                     No.  lb/A    A      C    J    K    L    M    BB   CC                          ______________________________________                                        37   0.5     100    100  100  100  100  100  98   80                               0.25    100    100  100  100  100  100  95   35                               0.125   100    100  100  100  100  100  85   10                               0.0625  100    99   99   100  100  99   55   10                               0.0313  99     70   85   95   99   90   45   0                                0.0156  80     35   65   70   90   55   15   0                                0.0078  85     70   75   90   75   60   20   ND                          39   0.5     100    100  100  100  100  100  100  98                               0.25    100    100  100  100  100  100  100  95                               0.125   100    100  100  100  100  100  99   85                               0.0625  100    100  100  100  100  100  90   40                               0.0313  100    100  100  100  100  100  80   35                               0.0156  100    99   99   100  95   99   35   25                               0.0078  95     60   90   99   75   65   10   0                           ______________________________________                                    

                  TABLE 2c                                                        ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd  Rate                                                                     No.  lb/A    A     C    D    E    F   L    N   BB   CC                        ______________________________________                                        38   0.5000  65    60   100  95   90  60   99  20   0                              0.2500  40    20   100  100  70  30   95  5    0                              0.1250  10    10   85   98   70  20   70  0    0                              0.0625  0     0    90   90   30  0    70  0    0                              0.0313  0     0    60   75   0   0    60  0    0                              0.0156  0     0    65   55   0   0    50  0    0                              0.0078  0     0    50   30   0   0    10  0    0                         ______________________________________                                    

                  TABLE 2d                                                        ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd  Rate                                                                     No.  1b/A    C      D    E    F    L    P    BB   CC                          ______________________________________                                        2    0.25    0      50   35   35   20   0    0    5                                0.0625  0      45   25   0    10   10   0    0                                0.0156  0      10   0    0    0    0    0    0                                1       15     70   60   15   25   0    0    45                               0.5     0      35   60   0    0    0    0    0                                0.25    0      20   30   0    0    0    0    0                                0.125   0      0    0    0    0    0    0    0                                0.063   0      0    0    0    0    0    0    0                                0.031   0      0    0    0    0    0    0    0                           3    0.25    15     25   60   5    25   5    0    20                               0.0625  0      0    0    0    0    0    0    5                                0.0156  0      0    0    0    0    0    0    0                                0.0039  0      0    0    0    0    0    0    0                           7    1       0      65   5    10   75   55   0    5                                0.25    0      0    0    0    25   15   0    0                                0.0625  0      0    0    0    0    0    0    0                           8    0.25    100    98   45   80   100  100  85   30                               0.0625  95     55   0    40   99   100  20   8                                0.0156  30     5    0    20   70   90   5    0                                0.5     100    ND   95   85   100  100  98   70                               0.25    100    ND   80   75   100  100  90   50                               0.125   100    ND   65   65   100  100  90   30                               0.063   100    ND   30   50   99   99   25   20                               0.031   60     ND   45   40   90   100  10   5                                0.016   45     ND   20   25   90   95   0    0                                0.25    100    100  100  99   100  100  70   80                               0.125   99     100  99   93   100  100  25   60                               0.063   88     93   60   63   93   100  23   30                               0.031   43     80   90   53   93   100  15   18                               0.016   20     60   45   10   58   93   3    15                               0.008   5      30   38   0    15   45   5    0                                0.25    100    100  100  75   100  100  100  45                               0.0625  100    95   85   40   100  100  70   10                               0.0156  55     85   50   20   90   98   15   0                                0.0039  0      65   0    0    65   90   5    0                                0.5     100    100  98   97   100  100  95   65                               0.25    100    100  98   85   100  100  85   40                               0.125   100    93   93   85   100  100  70   23                               0.0625  99     70   55   60   100  100  35   8                                0.0313  90     45   40   40   99   100  25   3                                0.0156  75     45   45   25   98   97   10   5                                0.0078  65     0    20   15   85   95   10   5                                0.0039  40     0    0    0    75   80   5    0                           9    0.25    95     98   5    10   85   65   7    0                                0.0625  75     85   10   0    65   25   0    0                                0.0156  0      50   0    0    15   0    0    0                           10   0.25    20     99   40   50   35   35   5    0                                0.0625  0      65   40   0    0    25   0    5                                0.0156  0      0    0    0    0    0    0    0                                0.0039  0      0    0    0    0    0    0    0                           11   0.25    98     99   45   40   98   98   25   7                                0.0625  80     85   30   25   85   80   5    0                                0.0156  0      50   15   35   20   5    0    0                                0.0039  0      10   0    0    0    0    0    0                           12   0.25    95     95   45   45   98   98   5    35                               0.0625  30     75   40   30   75   75   0    5                                0.0156  0      0    0    0    50   65   0    0                                0.0039  0      0    0    0    10   10   0    0                                0.5     95     97   95   80   98   99   15   25                               0.25    80     90   85   65   97   98   3    15                               0.125   40     85   75   30   80   90   3    0                                0.0625  35     50   25   35   85   85   0    0                                0.0313  10     10   0    0    45   85   0    0                                0.0156  5      0    0    0    30   75   0    0                                0.0078  0      0    0    0    10   20   0    0                                0.0039  0      0    0    0    10   20   0    0                           13   0.25    100    100  80   70   100  100  80   30                               0.0625  95     98   60   45   98   100  40   8                                0.0156  30     80   35   0    90   90   10   8                                0.0039  5      35   25   0    55   50   5    3                                0.5     100    100  97   90   100  100  85   55                               0.25    99     98   93   75   100  100  65   30                               0.125   98     95   80   70   100  100  40   15                               0.0625  90     80   75   65   99   99   35   5                                0.0313  55     55   20   30   98   95   5    3                                0.0156  30     35   0    10   85   95   3    5                                0.0078  15     10   0    5    60   85   3    0                                0.0039  0      0    0    0    25   25   0    0                           14   0.25    90     60   40   15   97   98   15   8                                0.0625  10     0    5    0    80   85   5    0                                0.0156  0      0    0    0    50   50   0    0                                0.0039  0      0    0    0    5    25   0    0                           15   0.25    100    97   93   90   100  100  93   20                               0.0625  98     65   65   40   100  100  30   15                               0.0156  45     5    10   5    97   90   20   10                               0.0039  0      10   20   5    35   55   5    0                           16   0.25    0      0    0    0    0    0    0    0                                0.0625  0      0    0    0    0    0    0    0                                0.0156  0      0    0    0    0    0    0    0                           17   0.25    0      50   50   10   5    40   0    5                                0.0625  0      55   0    0    0    15   0    0                                0.0156  0      25   0    0    0    0    0    0                           18   0.25    95     98   45   20   90   95   15   15                               0.0625  5      60   5    0    45   75   3    0                                0.0156  0      20   0    0    0    15   0    0                                1       100    100  95   70   99   100  80   80                               0.5     100    100  80   80   100  100  30   20                               0.25    99     98   55   25   95   100  25   0                                0.125   90     95   50   15   65   95   50   0                                0.063   55     90   55   20   70   80   0    0                                0.031   15     50   10   0    30   45   0    0                                0.25    93     100  100  53   85   99   65   40                               0.125   60     98   75   25   45   65   8    10                               0.063   10     93   55   20   10   30   5    10                               0.031   0      43   55   0    0    20   0    0                                0.016   0      50   25   10   0    0    3    0                                0.008   5      30   25   0    30   3    3    3                           19   0.25    98     90   35   60   95   99   25   10                               0.0625  70     55   10   25   85   98   5    3                                0.0156  15     15   0    15   20   55   0    0                                0.25    95     98   93   70   85   100  28   28                               0.125   65     100  95   75   85   99   13   13                               0.063   20     78   70   30   48   85   3    10                               0.031   0      45   30   0    20   73   3    10                               0.016   10     0    0    0    30   60   0    0                                0.008   0      0    0    0    5    0    0    0                           20   0.25    95     95   85   55   85   98   15   5                                0.0625  70     80   15   35   65   85   0    3                                0.0156  0      20   0    0    5    30   0    0                                0.5     85     ND   85   90   70   95   15   15                               0.25    35     ND   70   55   25   80   10   5                                0.125   10     ND   70   45   20   65   0    10                               0.063   10     ND   50   0    20   65   0    5                                0.031   0      ND   35   0    0    40   0    5                                0.016   0      ND   0    0    0    40   0    0                           21   0.25    90     25   20   20   85   45   10   15                               0.0625  35     10   15   0    85   40   0    0                                0.0156  0      0    0    0    5    10   0    0                           22   0.25    95     40   5    25   97   98   5    25                               0.0625  25     10   0    0    70   55   0    3                                0.0156  0      0    0    0    0    0    0    0                           23   0.25    40     65   25   10   30   65   0    5                                0.0625  0      5    0    5    0    0    0    0                                0.0156  0      0    0    0    0    0    0    0                           24   0.25    20     60   0    40   10   35   0    0                                0.0625  0      10   0    0    0    0    0    0                                0.0156  0      0    0    0    0    0    0    0                           25   0.25    95     80   55   35   99   100  45   5                                0.0625  90     80   30   25   90   98   10   0                                0.0156  25     25   0    10   35   85   5    0                                0.0039  0      0    0    0    20   10   0    0                           26   0.25    100    100  90   85   100  99   97   25                               0.0625  98     97   65   35   98   97   65   0                                0.0156  75     75   20   25   70   75   10   0                                0.0039  10     40   10   10   35   25   3    0                                0.5     100    100  99   99   100  100  98   60                               0.25    100    100  97   93   100  100  95   75                               0.125   100    100  80   88   100  100  85   53                               0.063   100    97   60   65   100  100  50   18                               0.031   95     97   43   53   90   87   10   5                                0.016   85     93   30   40   85   90   8    5                                0.25    100    100  98   92   100  99   33   72                               0.125   100    100  100  90   100  100  70   73                               0.063   98     100  90   68   97   100  25   25                               0.031   70     83   73   30   75   65   18   18                               0.016   35     83   58   25   43   50   8    3                                0.008   0      15   13   10   0    15   0    0                           27   0.25    60     90   75   20   90   50   5    3                                0.0625  10     70   65   0    20   0    3    0                                0.0156  0      30   0    0    0    0    0    0                                0.0039  0      0    0    0    0    0    0    0                           28   0.25    15     45   0    10   50   30   3    0                                0.0625  0      0    0    0    20   20   0    0                                0.0156  0      20   0    0    0    0    0    0                                0.0039  0      25   0    0    0    0    0    0                           29   0.25    80     70   65   15   100  95   30   20                               0.0625  30     30   20   0    90   90   0    20                               0.0156  0      10   0    0    10   10   0    0                                0.0039  0      0    0    0    0    0    0    0                           30   0.25    70     90   20   25   95   25   15   20                               0.0625  5      70   30   10   90   25   3    5                                0.0156  10     10   0    0    30   10   0    5                                0.0039  0      0    0    0    15   0    0    0                           31   0.25    5      80   45   15   40   10   10   3                                0.0625  0      20   15   0    45   20   15   0                                0.0156  0      5    0    0    0    0    0    0                                0.0039  0      0    0    0    0    0    0    0                           32   0.25    5      25   10   25   85   65   5    8                                0.0625  0      0    5    0    30   10   3    0                                0.0156  0      20   35   0    25   0    10   5                                0.0039  0      0    0    0    25   0    0    0                           33   0.25    65     85   25   35   90   65   10   5                                0.0625  15     25   0    35   35   20   0    0                                0.0156  0      0    0    0    0    0    0    0                                0.25    0      55   0    10   0    0    0    0                                0.125   0      0    0    0    0    0    0    0                                0.063   0      0    0    0    0    0    0    0                                0.031   0      0    0    0    0    0    0    0                                0.016   0      0    0    0    0    0    0    0                                0.008   0      0    0    0    0    0    0    0                                1       99     100  98   50   99   95   45   20                               0.5     95     100  98   65   98   95   20   10                               0.25    70     100  80   50   95   95   10   5                                0.125   35     95   70   30   70   95   5    5                                0.063   45     100  ND   40   60   85   5    5                                0.031   40     100  ND   60   55   90   10   5                                0.016   ND     100  ND   ND   ND   ND   15   0                           37   0.5     100    100  100  95   100  100  100  70                               0.25    100    100  98   60   100  100  98   40                               0.125   100    100  80   55   99   100  90   5                                0.0625  99     85   75   30   98   100  80   0                                0.0313  70     90   0    0    99   99   30   0                                0.0156  15     60   ND   0    70   98   15   0                                0.0078  0      0    0    0    15   80   0    0                           38   0.5     10     80   85   75   35   50   5    0                                0.25    0      80   95   85   25   20   0    0                                0.125   0      50   80   25   0    0    0    0                                0.0625  0      0    75   0    0    0    0    0                                0.0313  0      0    0    0    0    0    0    0                                0.0156  0      0    0    0    0    0    0    0                                0.0078  0      0    0    0    0    0    0    0                           41   0.25    50     90   0    25   50   40   0    0                                0.0625  0      20   0    0    0    0    0    0                           42   0.25    35     65   60   65   0    0    5    0                                0.0625  30     0    0    0    0    0    5    0                           43   0.25    15     65   10   45   35   15   0    0                                0.0625  0      0    50   0    0    0    10   0                           44   0.25    10     60   50   0    40   50   0    0                                0.0625  55     0    30   0    10   5    0    0                           45   0.25    75     98   30   50   98   100  0    0                                0.0625  25     60   35   50   95   95   0    0                           46   0.25    0      80   20   10   75   40   0    0                                0.0625  0      20   0    0    55   35   0    0                           47   0.25    75     50   70   0    50   75   0    0                                0.0625  25     25   65   0    25   20   0    0                           48   0.25    100    95   99   45   98   99   35   0                                0.0625  85     65   40   20   65   60   3    0                           49   0.25    75     0    40   0    45   10   0    0                                0.0625  25     0    65   0    0    0    0    0                           50   0.25    25     40   0    0    0    0    0    0                                0.0625  0      0    15   0    0    0    0    0                           51   0.25    50     90   15   0    80   90   8    3                                0.0625  0      80   15   0    50   40   0    0                           52   0.25    100    100  70   65   100  100  75   5                                0.0625  100    100  100  45   99   100  45   0                           53   0.25    85     85   80   15   75   9    5    0                                0.0625  70     85   60   45   60   70   8    5                           54   0.25    100    100  40   35   99   99   10   5                                0.0625  75     85   70   0    75   80   0    0                           55   0.25    30     85   10   30   95   100  0    0                                0.0625  65     0    0    0    90   80   5    0                           56   0.25    100    100  80   20   80   90   0    0                                0.0625  40     100  80   25   35   55   3    0                           57   0.25    50     90   90   10   15   10   0    0                                0.0625  20     90   75   5    0    0    15   0                           58   0.25    100    100  100  75   100  100  20   25                               0.0625  99     85   55   10   85   90   3    15                          ______________________________________                                    

                  TABLE 3a                                                        ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd    Rate                                                                   No.    1b/A       G      H        I    DD                                     ______________________________________                                        1      4.5        15     0        0    10                                            0.893      0      0        0    0                                             0.1785     0      0        0    0                                      34     4.5        25     0        10   5                                             0.893      0      0        0    0                                             0.1785     0      0        0    0                                      35     4.5        80     95       100  10                                            0.893      35     35       100  0                                             0.1785     0      0        30   0                                      36     0.893      100    100      100  25                                            0.1785     75     0        100  10                                            0.0357     0      0        20   0                                             0.0071     0      0        0    0                                             0.893      50     30       100  10                                            0.1785     0      25       80   0                                             0.0357     0      70       0    0                                             0.0071     0      0        0    0                                      37     0.893      100    100      100  100                                           0.1786     100    90       100  70                                            0.0357     70     20       85   10                                            0.0071     0      0        0    0                                      38     0.893      20     100      100  0                                             0.1785     15     98       100  15                                            0.0357     0      90       100  0                                             0.0071     0      20       45   0                                      39     0.893      100    100      100  100                                           0.1785     100    100      100  80                                            0.0357     100    100      100  15                                            0.0071     10     85       25   0                                      40     4.5        100    90       100  70                                            0.893      20     0        30   0                                             0.1785     0      0        0    0                                             0.0357     0      0        0    0                                      ______________________________________                                    

                                      TABLE 3b                                    __________________________________________________________________________    PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                            Cpd                                                                              Rate                                                                       No.                                                                              lb/A                                                                              G  H   I  O  T   U  V  EE  DD                                          __________________________________________________________________________    2  0.25                                                                              15 60  50 25 15  25 55 20  7                                              0.0625                                                                            5  60  25 10 5   10 15 5   0                                              0.0156                                                                            5  60  35 30 10  15 50 10  0                                           3  0.25                                                                              5  0   5  30 5   0  0  5   0                                              0.0625                                                                            0  0   0  0  0   0  10 0   0                                              0.0156                                                                            0  0   0  5  0   0  0  0   0                                              0.0039                                                                            0  0   0  5  0   0  5  0   0                                           7  1   40 15  35 50 10  35 15 0   8                                              0.25                                                                              0  0   5  0  0   0  0  0   0                                              0.0625                                                                            0  0   0  0  0   0  0  0   0                                           8  0.25                                                                              100                                                                              100 90 100                                                                              95  100                                                                              100                                                                              98  0                                              0.0625                                                                            100                                                                              100 35 100                                                                              45  75 100                                                                              65  0                                              0.0156                                                                            75 85  20 100                                                                              20  20 100                                                                              25  0                                              0.5 100                                                                              100 100                                                                              100                                                                              100 100                                                                              ND 100 30                                             0.25                                                                              100                                                                              100 100                                                                              100                                                                              100 100                                                                              ND 100 15                                             0.125                                                                             100                                                                              100 100                                                                              100                                                                              100 100                                                                              ND 100 0                                              0.0625                                                                            100                                                                              100 100                                                                              100                                                                              90  85 ND 85  0                                              0.0313                                                                            100                                                                              100 100                                                                              100                                                                              90  97 ND 50  0                                              0.0156                                                                            95 100 90 90 50  50 ND 50  0                                              0.0078                                                                            100                                                                              100 75 100                                                                              75  65 ND 60  0                                              0.5 100                                                                              100 100                                                                              100                                                                              100 100                                                                              100                                                                              95  10                                             0.25                                                                              100                                                                              100 100                                                                              100                                                                              100 99 100                                                                              90  0                                              0.125                                                                             100                                                                              100 100                                                                              100                                                                              97  95 100                                                                              90  0                                              0.0625                                                                            100                                                                              100 99 100                                                                              95  90 100                                                                              65  0                                              0.0313                                                                            100                                                                              99  65 100                                                                              85  75 100                                                                              45  0                                              0.0156                                                                            97 95  80 100                                                                              70  40 99 40  0                                              0.0078                                                                            88 75  65 100                                                                              30  30 97 20  0                                              0.0039                                                                            45 30  30 100                                                                              10  15 95 10  0                                           9  0.25                                                                              80 90  20 100                                                                              5   5  90 30  0                                              0.0625                                                                            40 20  5  100                                                                              0   0  90 25  0                                              0.0156                                                                            30 15  5  70 0   0  40 5   0                                           10 0.25                                                                              20 5   30 98 5   25 80 50  0                                              0.0625                                                                            5  0   5  60 0   0  65 5   0                                              0.0156                                                                            0  5   0  10 0   0  55 5   0                                              0.0039                                                                            0  0   0  15 0   0  65 10  0                                           11 0.25                                                                              60 25  75 100                                                                              20  10 95 15  0                                              0.0625                                                                            20 25  10 75 0   5  60 5   0                                              0.0156                                                                            25 15  5  10 0   5  65 5   0                                              0.0039                                                                            15 35  10 5  0   5  60 0   0                                           12 0.25                                                                              60 85  65 98 60  60 80 15  5                                              0.0625                                                                            55 75  60 98 40  35 80 10  0                                              0.0156                                                                            35 45  20 95 15  15 30 5   0                                              0.0039                                                                            25 15  10 70 5   5  35 0   0                                           13 0.25                                                                              98 90  100                                                                              100                                                                              95  100                                                                              90 65  3                                              0.0625                                                                            98 90  90 100                                                                              75  65 90 45  2                                              0.0156                                                                            65 25  50 100                                                                              25  25 30 10  0                                              0.0039                                                                            20 20  10 98 5   5  25 0   0                                           14 0.25                                                                              65 98  20 100                                                                              50  30 98 5   2                                              0.0625                                                                            25 80  5  85 5   5  25 0   0                                              0.0156                                                                            10 85  5  30 5   10 25 0   0                                              0.0039                                                                            5  85  0  50 5   5  5  5   0                                           15 0.25                                                                              100                                                                              100 98 100                                                                              90  100                                                                              100                                                                              60  0                                              0.0625                                                                            80 100 65 100                                                                              90  70 80 15  0                                              0.0156                                                                            30 90  10 100                                                                              40  15 35 10  0                                              0.0039                                                                            30 75  0  100                                                                              5   5  55 5   0                                           16 0.25                                                                              15 95  45 10 20  20 100                                                                              55  0                                              0.0625                                                                            10 95  45 15 10  25 95 85  0                                              0.0156                                                                            5  80  75 15 15  20 80 10  0                                           17 0.25                                                                              20 100 100                                                                              35 15  30 100                                                                              90  0                                              0.0625                                                                            15 70  55 20 10  25 98 45  0                                              0.0156                                                                            30 75  45 60 5   10 80 20  0                                           18 0.25                                                                              95 100 100                                                                              100                                                                              80  85 100                                                                              100 0                                              0.0625                                                                            70 65  50 100                                                                              25  15 98 55  0                                              0.0156                                                                            25 25  5  100                                                                              10  20 98 20  0                                           19 0.25                                                                              95 100 80 100                                                                              75  40 100                                                                              50  0                                              0.0625                                                                            80 85  35 100                                                                              25  35 100                                                                              25  0                                              0.0156                                                                            35 15  10 100                                                                              20  20 95 40  0                                           20 0.25                                                                              70 100 100                                                                              100                                                                              25  65 100                                                                              95  0                                              0.0625                                                                            25 98  75 100                                                                              20  25 100                                                                              45  0                                              0.0156                                                                            25 98  55 100                                                                              10  30 95 30  0                                           21 0.25                                                                              95 98  90 100                                                                              60  35 100                                                                              90  5                                              0.0625                                                                            65 80  60 90 5   10 70 20  0                                              0.0156                                                                            15 65  15 25 5   5  30 10  0                                           22 0.25                                                                              85 100 100                                                                              100                                                                              85  40 100                                                                              90  6                                              0.0625                                                                            40 60  45 85 20  10 100                                                                              15  5                                              0.0156                                                                            25 55  40 85 10  10 60 10  0                                           23 0.25                                                                              15 100 45 85 10  15 100                                                                              75  0                                              0.0625                                                                            35 25  15 100                                                                              5   20 50 15  0                                              0.0156                                                                            10 25  45 55 10  35 85 15  3                                           24 0.25                                                                              50 100 95 100                                                                              15  30 100                                                                              95  7                                              0.0625                                                                            25 70  35 15 5   10 40 20  0                                              0.0156                                                                            20 65  40 10 5   20 80 25  0                                           25 0.25                                                                              98 100 85 100                                                                              90  10 100                                                                              35  0                                              0.0625                                                                            90 90  35 98 25  10 85 35  0                                              0.0156                                                                            60 50  35 95 0   0  65 10  0                                              0.0039                                                                            55 25  0  80 0   0  25 5   0                                           26 0.25                                                                              95 100 80 100                                                                              65  55 100                                                                              40  0                                              0.0625                                                                            70 90  35 100                                                                              10  5  100                                                                              20  0                                              0.0156                                                                            20 60  15 100                                                                              0   0  80 15  0                                              0.0039                                                                            10 25  5  45 0   0  35 10  0                                           27 0.25                                                                              35 75  65 100                                                                              5   5  35 10  0                                              0.0625                                                                            15 35  35 70 0   5  30 5   0                                              0.0156                                                                            5  25  5  35 0   0  20 0   0                                              0.0039                                                                            10 15  0  25 0   0  65 0   0                                           28 0.25                                                                              30 25  40 90 0   0  70 5   0                                              0.0625                                                                            15 10  15 45 0   0  45 0   0                                              0.0156                                                                            15 5   5  40 0   0  45 0   0                                              0.0039                                                                            15 15  5  40 0   0  35 0   0                                           29 0.25                                                                              40 90  70 95 15  10 70 15  0                                              0.0625                                                                            10 30  40 50 0   5  65 0   0                                              0.0156                                                                            5  40  30 50 0   5  30 5   0                                              0.0039                                                                            5  0   5  35 0   5  55 5   0                                           30 0.25                                                                              20 35  40 98 0   5  50 5   0                                              0.0625                                                                            10 15  10 60 0   5  50 5   0                                              0.0156                                                                            5  20  5  35 0   5  15 0   0                                              0.0039                                                                            0  5   5  15 0   0  5  0   0                                           31 0.25                                                                              5  25  30 20 5   5  25 5   0                                              0.0625                                                                            5  20  15 5  0   0  20 5   0                                              0.0156                                                                            0  5   10 5  0   5  35 0   0                                              0.0039                                                                            0  5   0  5  0   0  15 0   0                                           32 0.25                                                                              10 5   5  40 0   0  45 5   0                                              0.0625                                                                            0  10  0  25 5   0  30 0   0                                              0.0156                                                                            0  35  2  50 0   0  55 5   0                                              0.0039                                                                            0  25  5  0  0   0  40 0   0                                           33 0.25                                                                              40 30  45 50 5   10 55 10  0                                              0.0625                                                                            10 20  20 10 0   5  20 5   0                                              0.0156                                                                            15 30  35 20 0   10 50 0   0                                           41 0.25                                                                              15 55  60 100                                                                              10  30 100                                                                              5   3                                              0.0625                                                                            10 20  35 98 5   10 95 0   0                                           42 0.25                                                                              15 40  80 95 5   10 30 5   0                                              0.0625                                                                            5  0   0  70 0   0  5  0   0                                           43 0.25                                                                              10 55  20 60 5   5  60 5   0                                              0.0625                                                                            5  5   0  20 0   5  5  0   0                                           44 0.25                                                                              20 85  40 100                                                                              5   5  85 20  0                                              0.0625                                                                            5  30  60 80 0   5  75 0   0                                           45 0.25                                                                              100                                                                              80  98 100                                                                              80  98 100                                                                              5   0                                              0.0625                                                                            30 35  50 100                                                                              20  45 98 0   0                                           46 0.25                                                                              10 90  75 80 5   15 80 5   0                                              0.0625                                                                            5  60  50 7  50  10 70 0   0                                           47 0.25                                                                              25 70  95 100                                                                              5   20 70 5   0                                              0.0625                                                                            15 10  45 85 0   10 10 5   0                                           48 0.25                                                                              60 95  45 100                                                                              45  90 100                                                                              5   0                                              0.0625                                                                            15 15  10 100                                                                              10  20 70 10  0                                           49 0.25                                                                              5  5   5  60 5   5  55 0   0                                              0.0625                                                                            5  0   5  30 0   5  40 0   0                                           50 0.25                                                                              5  35  25 10 0   5  35 0   0                                              0.0625                                                                            0  5   0  25 0   5  25 0   0                                           51 0.25                                                                              20 70  55 100                                                                              15  35 90 5   0                                              0.0625                                                                            10 10  5  100                                                                              5   5  55 5   0                                           52 0.25                                                                              100                                                                              95  90 100                                                                              85  100                                                                              95 60  0                                              0.0625                                                                            80 80  80 100                                                                              40  75 80 20  0                                           53 0.25                                                                              15 40  50 100                                                                              5   15 70 5   0                                              0.0625                                                                            35 10  90 100                                                                              10  25 80 10  0                                           54 0.25                                                                              35 90  80 100                                                                              30  75 98 0   5                                              0.0625                                                                            15 70  20 100                                                                              10  10 75 0   0                                           55 0.25                                                                              60 75  85 100                                                                              35  55 100                                                                              5   0                                              0.0625                                                                            15 15  0  95 0   15 75 0   0                                           56 0.25                                                                              75 95  90 100                                                                              55  100                                                                              100                                                                              5   5                                              0.0625                                                                            40 65  60 200                                                                              25  40 70 0   0                                           57 0.25                                                                              15 20  80 85 5   20 60 0   0                                              0.0625                                                                            5  5   5  50 0   5  5  0   0                                           58 0.25                                                                              95 100 95 100                                                                              75  100                                                                              100                                                                              50  5                                              0.0625                                                                            50 45  45 100                                                                              25  35 80 5   0                                           __________________________________________________________________________

Post-Emergence Herbicide Tests

The post-emergence herbicidal activity of some of the various compoundsof this invention was demonstrated by greenhouse testing in thefollowing manner.

Topsoil was placed in aluminum pans having holes in the bottom andcompacted to a depth of 1.3 to 1.6 cm from the top of the pan. Apredetermined number of seeds of each of several dicotyledonous andmonocotyledonous annual plant species and/or vegetative propagules forthe perennial plant species were placed on the soil and pressed into thesoil surface. The seeds and/or vegetative propagules were covered withsoil and leveled. The pans were then placed on a bench in the greenhouseand watered either from overheard irrigation or by subirrigation asneeded. After the plants reach the desired age (two to three weeks),each pan, is removed individually to a spraying chamber and sprayed bymeans of an atomizer, operating at a spray pressure of 170.3 kPa (10psig) at the application rates noted. In the spray solution was anamount of an emulsifying agent mixture to give a spray solution orsuspension which contains about 0.4% by volume of the emulsifier. Thespray solution or suspension contained a sufficient amount of thecandidate chemical in order to give application rates of the activeingredient corresponding to those shown in Tables 4 and 5, whileapplying a total amount of solution or suspension equivalent to 1870L/Ha (200 gallons/acre). The pans were returned to the greenhouse andwatered as before and the injury to the plants as compared to thecontrol was observed at approximately 10-14 days (usually 11 days) andin some instances observed again at 24-28 days (usually 25 days) afterspraying. The post-emergent herbicidal activity shown in these tables isthe percent inhibition of each plant species. Testing with warm seasonand cool season plants is shown in tables 4a-4d and 3a-3b, respectively.Table subdivisions a through d represent different spectra of plantstested.

                                      TABLE 4a                                    __________________________________________________________________________    POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd                                                                              Rate                                                                       No.                                                                              lb/A                                                                              A  B   C  D  E   F  G  BB  CC                                          __________________________________________________________________________    1  4.5 50 30  0  20 15  0  0  40  0                                              0.893                                                                             0  0   0  0  0   0  0  0   0                                              0.1785                                                                            0  0   0  0  0   0  0  0   0                                           34 4.5 0  0   10 20 55  25 0  15  15                                             0.893                                                                             0  0   0  0  0   0  0  0   10                                             0.1785                                                                            0  0   0  0  0   0  0  0   0                                           35 4.5 65 0   65 100                                                                              95  90 0  75  55                                             0.893                                                                             15 0   20 75 85  5  50 60  30                                             0.1785                                                                            0  0   0  50 65  0  0  30  20                                             0.893                                                                             35 0   0  70 100 15 0  25  55                                             0.1785                                                                            20 0   0  45 75  0  0  20  25                                             0.0357                                                                            0  0   0  0  0   0  0  0   0                                              0.0071                                                                            0  0   0  0  0   0  0  0   0                                           36 0.893                                                                             70 25  50 100                                                                              100 98 0  40  45                                             0.1785                                                                            45 0   45 75 85  60 0  30  35                                             0.0357                                                                            10 0   0  70 40  0  0  25  25                                             0.0071                                                                            0  0   0  65 20  75 0  0   15                                          37 0.893                                                                             65 40  45 100                                                                              100 80 15 100 60                                             0.1785                                                                            65 15  65 80 95  55 10 80  40                                             0.0357                                                                            20 10  15 35 45  40 0  10  40                                             0.0071                                                                            0  0   0  25 0   5  0  5   10                                          38 0.893                                                                             15 25  15 100                                                                              100 100                                                                              0  25  25                                             0.1785                                                                            10 25  15 100                                                                              100 80 10 25  30                                             0.0357                                                                            35 25  10 100                                                                              100 80 0  10  20                                             0.0071                                                                            0  35  10 65 80  80 0  5   10                                          39 0.893                                                                             100                                                                              30  98 100                                                                              95  100                                                                              70 95  100                                            0.1785                                                                            100                                                                              10  98 100                                                                              100 80 25 100 70                                             0.0357                                                                            100                                                                              40  70 100                                                                              80  98 35 30  70                                             0.0071                                                                            65 0   30 75 95  80 10 50  25                                          40 4.5 100                                                                              0   85 100                                                                              100 100                                                                              30 50  80                                             0.893                                                                             10 0   65 100                                                                              80  70 50 85  70                                             0.1785                                                                            0  55  0  75 70  65 0  45  30                                             0.0357                                                                            0  70  0  55 50  80 0  25  25                                          __________________________________________________________________________

                  TABLE 4b                                                        ______________________________________                                        POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd    Rate                                                                   No.    lb/A    C       D   E     F   P     BB  CC                             ______________________________________                                        37     0.0625  50      55  60    50  45    45  70                                    0.0313  40      40  40    40  45    35  45                                    0.0156  35      40  40    40  40    35  30                                    0.078   0       15  20    10  0     0   0                                     0.0039  0       0   0     0   0     0   0                              ______________________________________                                    

                  TABLE 4c                                                        ______________________________________                                        POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd  Rate                                                                     No.  lb/A    D      E    F    N   Q   R    S    BB  CC                        ______________________________________                                        38   0.25    100    95   100  50  20  100  100  10  15                             0.125   99     98   100  0   0   100  99   10  10                             0.0625  100    100  99   0   0   100  99   10  5                              0.0313  80     90   99   0   0   100  80   5   5                              0.0156  70     90   90   0   0   100  65   5   0                              0.078   65     85   70   0   0   100  70   5   0                         ______________________________________                                    

                  TABLE 4d                                                        ______________________________________                                        POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd  Rate                                                                     No.  1b/A    C     D     E    F    L    P     BB  CC                          ______________________________________                                        2    0.25    15    85    45   70   20   0     3   20                               0.0625  0     45    15   65   0    0     2   10                               0.0156  0     10    5    15   0    0     0   5                           3    0.25    0     85    25   65   0    0     2   15                               0.0625  0     10    0    15   0    0     0   3                                0.0156  0     0     0    0    0    0     0   0                                0.0039  0     0     0    0    0    0     0   0                           7    1       0     25    20   5    30   0     0   20                               0.25    0     5     0    0    0    0     0   5                                0.0625  0     20    0    0    0    0     0   0                           8    0.25    40    90    40   75   70   30    15  35                               0.0625  15    90    30   70   55   15    8   25                               0.0156  0     75    5    65   5    0     2   5                                0.25    85    99    95   99   90   80    20  75                               0.0625  30    90    60   75   35   35    8   25                               0.0156  5     70    65   45   15   5     5   15                               0.0039  0     50    55   40   0    0     2   10                          9    0.25    25    95    45   35   20   10    10  60                               0.0625  10    80    20   25   5    0     5   15                               0.0156  0     65    15   5    20   5     2   20                          10   0.25    5     90    35   55   15   15    3   8                                0.0625  0     75    15   40   5    5     2   7                                0.0156  0     35    5    25   0    0     0   5                                0.0039  0     25    0    0    0    0     0   0                           11   0.25    0     50    25   15   5    0     15  20                               0.0625  5     25    5    15   5    0     3   7                                0.0156  0     5     5    5    0    0     0   5                                0.0039  0     5     0    0    0    0     0   5                           12   0.25    80    99    99   98   65   35    15  85                               0.0625  40    95    95   80   55   20    8   35                               0.0156  10    95    90   80   25   0     10  20                               0.0039  5     80    70   70   5    5     5   20                          13   0.25    90    100   98   95   100  95    55  90                               0.0625  80    100   95   95   98   90    25  75                               0.0156  10    95    85   95   65   20    20  40                               0.0039  5     85    70   65   35   5     5   25                          14   0.25    65    99    85   95   80   25    10  25                               0.0625  5     90    75   85   65   35    8   20                               0.0156  0     65    35   35   55   5     2   15                               0.0039  5     65    25   10   45   5     5   15                          15   0.25    99    100   98   99   100  90    65  90                               0.0625  65    99    98   95   100  93    20  65                               0.0156  5     95    65   75   85   10    10  35                               0.0039  0     80    65   75   70   5     8   10                          16   0.25    0     0     5    0    0    0     0   0                                0.0625  0     0     0    0    0    0     0   0                                0.0156  0     0     0    0    0    0     0   0                           17   0.25    70    99    90   95   65   45    10  30                               0.0625  35    95    65   85   20   10    8   15                               0.0156  15    70    20   65   5    0     2   10                          18   0.25    5     90    50   65   35   5     15  40                               0.0625  0     65    15   40   10   0     3   30                               0.0156  0     60    15   3    0    0     2   5                           19   0.25    65    90    35   75   80   65    20  50                               0.0625  5     70    20   65   35   5     5   15                               0.0156  0     40    10   40   10   0     3   10                          20   0.25    85    100   98   90   80   75    8   35                               0.0625  80    99    80   90   85   55    7   35                               0.0156  20    99    65   80   60   25    5   15                          21   0.25    25    90    90   65   35   35    10  35                               0.0625  20    45    50   25   25   15    5   25                               0.0156  35    55    15   55   35   35    3   10                          22   0.25    30    90    40   65   60   75    5   50                               0.0625  20    55    30   65   20   25    5   20                               0.0156  15    40    25   45   20   15    3   5                           23   0.25    60    98    65   90   65   20    7   30                               0.0625  25    80    60   75   35   20    7   20                               0.0156  0     70    20   65   10   0     3   5                           24   0.25    15    99    75   85   20   15    10  45                               0.0625  10    98    65   75   10   5     10  35                               0.0156  5     69    25   55   5    0     7   15                          25   0.25    85    100   90   90   85   75    20  60                               0.0625  35    100   70   65   35   60    15  30                               0.0156  5     90    60   50   25   20    5   25                               0.0039  0     65    15   5    20   5     0   20                          26   0.25    95    99    80   85   80   45    25  75                               0.0625  65    98    70   80   75   10    15  50                               0.0156  30    80    35   50   45   5     7   20                               0.0039  5     75    45   15   20   0     3   10                          27   0.25    70    98    95   80   90   35    65  80                               0.0625  35    80    75   65   35   20    20  60                               0.0156  5     65    75   35   35   5     20  25                               0.0039  5     10    35   15   15   0     15  20                          28   0.25    10    60    65   40   20   25    40  20                               0.0625  0     25    20   20   35   5     20  15                               0.0156  0     20    15   25   20   0     5   15                               0.0039  0     15    15   15   10   5     20  35                          29   0.25    90    99    90   90   90   65    20  90                               0.0625  40    95    65   75   70   55    8   80                               0.0156  5     95    75   70   25   5     5   35                               0.0039  15    70    45   45   20   0     5   20                          30   0.25    60    85    65   60   70   20    20  65                               0.0625  15    70    35   50   35   20    8   30                               0.0156  5     65    5    20   10   5     5   15                               0.0039  5     35    0    15   0    0     3   15                          31   0.25    70    99    80   99   90   50    50  35                               0.0625  50    98    65   80   75   40    50  15                               0.0156  35    85    35   75   20   0     7   10                               0.0039  20    75    25   65   10   0     2   7                           32   0.25    35    85    40   65   45   45    15  20                               0.0625  15    65    20   45   25   25    3   15                               0.0156  0     25    0    15   15   15    2   7                                0.0039  0     10    0    10   0    0     2   5                           33   0.25    0     10    10   0    0    0     0   15                               0.0625  0     0     5    0    0    0     0   5                                0.0156  0     15    5    0    0    0     0   0                           41   0.25    65    99    75   95   70   5     35  15                               0.9625  15    98    70   85   55   15    5   10                          42   0.25    65    98    70   85   45   0     25  10                               0.0625  10    98    40   60   35   0     5   7                           43   0.25    5     80    75   85   25   0     7   15                               0.0625  5     65    15   70   10   0     10  5                           44   0.25    90    99    80   99   60   65    15  10                               0.0625  15    90    75   90   25   0     3   8                           45   0.25    75    100   80   100  95   80    55  35                               0.0625  55    100   90   85   80   35    10  20                          46   0.25    50    98    70   85   25   0     15  15                               0.0625  10    90    35   75   15   0     15  7                           47   0.25    5     100   70   100  50   5     50  30                               0.0625  20    90    40   80   25   5     5   8                           48   0.25    60    100   75   90   85   99    7   70                               0.0625  45    99    80   80   90   95    7   45                          49   0.25    0     10    5    50   5    0     5   5                                0.0625  0     25    0    30   0    0     5   5                           50   0.25    5     90    35   60   0    0     5   7                                0.0625  5     40    5    50   0    0     3   7                           51   0.25    60    100   35   85   85   85    7   65                               0.0625  30    99    30   75   20   45    5   45                          52   0.25    99    100   99   100  99   100   15  95                               0.0625  55    100   85   99   100  99    10  65                          53   0.25    70    100   99   100  75   75    7   75                               0.0625  25    95    50   75   25   15    5   40                          54   0.25    95    100   80   99   90   90    35  80                               0.0625  65    99    50   85   70   35    7   20                          55   0.25    45    99    85   90   70   35    20  20                               0.0625  20    90    35   65   15   0     10  15                          56   0.25    80    100   80   99   95   100   35  90                               0.0625  60    99    95   95   85   90    7   65                          57   0.25    35    100   50   85   35   15    3   17                               0.0625  15    90    35   70   20   5     2   20                          58   0.25    85    100   100  99   95   95    20  85                               0.0625  65    100   85   99   90   90    5   45                          ______________________________________                                    

                  TABLE 5a                                                        ______________________________________                                        POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd    Rate                                                                   No.    1b/A       G      H        I    DD                                     ______________________________________                                        1      4.5        35     40       30   10                                            0.893      0      0        0    0                                             0.1785     0      0        0    0                                      34     4.5        30     0        80   10                                            0.893      0      0        0    0                                             0.1785     0      0        0    0                                      35     4.5000     45     35       85   25                                            0.8930     35     10       75   20                                            0.1785     0      0        0    0                                             0.8930     35     0        95   15                                            0.1785     15     0        75   5                                             0.0357     0      0        25   0                                             0.0071     0      0        0    0                                      36     0.8930     60     65       75   25                                            0.1785     25     35       50   20                                            0.0357     10     15       25   5                                             0.0071     0      85       0    10                                     37     0.8930     85     80       90   30                                            0.1785     65     70       75   10                                            0.0357     25     40       35   0                                             0.0071     10     0        20   5                                      38     0.8930     5      98       85   10                                            0.1785     30     95       90   10                                            0.0357     25     75       85   10                                            0.0071     0      65       35   10                                     39     0.8930     100    100      100  75                                            0.1785     95     100      100  15                                            0.0357     80     100      100  0                                             0.0071     0      0        0    0                                      40     4.5000     100    98       100  25                                            0.8930     65     98       98   20                                            0.1785     35     80       60   15                                            0.0357     0      15       20   0                                      ______________________________________                                    

                                      TABLE 5b                                    __________________________________________________________________________    POSTEMERGENCE TESTS                                                           % PLANT INHIBITION                                                            Cpd                                                                              Rate                                                                       No.                                                                              1b/A                                                                              G   H  I   O  T   U  V   EE DD                                         __________________________________________________________________________    2  0.25                                                                              10  70 50  15 0   0  80  0  0                                             0.0625                                                                            0   20 15  0  0   0  65  0  0                                             0.0156                                                                            0   0  0   0  0   0  50  0  0                                          3  0.25                                                                              0   25 15  10 5   0  75  10 8                                             0.0625                                                                            0   5  5   0  0   0  65  5  0                                             0.0156                                                                            0   5  5   0  0   0  15  5  0                                             0.0039                                                                            0   5  5   5  0   0  25  0  0                                          7  1   15  5  80  55 20  25 75  5  17                                            0.25                                                                              5   0  35  20 5   5  65  0  5                                             0.0625                                                                            0   0  5   5  0   0  60  5  0                                          8  0.25                                                                              5   40 60  20 25  30 55  25 12                                            0.0625                                                                            20  25 35  15 20  20 45  5  6                                             0.0156                                                                            10  25 20  10 15  10 35  5  5                                             0.25                                                                              85  100                                                                              95  90 80  85 100 65 40                                            0.125                                                                             55  80 90  90 75  60 95  65 20                                            0.0625                                                                            70  85 85  65 60  50 85  30 10                                            0.0313                                                                            25  15 70  50 30  40 50  10 5                                             0.0156                                                                            40  10 65  40 20  15 45  5  5                                             0.0078                                                                            25  5  60  55 10  15 40  15 7                                             0.5 98  100                                                                              98  100                                                                              98  98 100 100                                                                              75                                            0.25                                                                              97  100                                                                              95  97 97  97 100 100                                                                              60                                            0.125                                                                             93  88 80  95 75  70 99  97 40                                            0.0625                                                                            90  80 70  80 70  60 99  95 30                                            0.0313                                                                            70  95 65  45 40  40 85  65 25                                            0.0156                                                                            75  65 55  50 30  35 70  75 18                                            0.0078                                                                            50  50 40  35 15  10 50  15 12                                            0.0039                                                                            45  75 45  30 5   10 55  20 10                                         9  0.25                                                                              20  15 50  20 25  25 35  20 13                                            0.0625                                                                            10  10 20  15 10  10 10  5  5                                             0.0156                                                                            5   15 15  15 5   5  10  0  0                                          10 0.25                                                                              20  15 25  50 10  25 90  35 10                                            0.0625                                                                            10  5  15  40 10  15 55  15 7                                             0.0156                                                                            5   5  10  10 0   5  40  5  0                                             0.0039                                                                            0   5  5   5  0   5  25  0  0                                          11 0.25                                                                              15  10 50  25 5   10 60  5  6                                             0.0625                                                                            5   0  50  20 0   5  25  0  0                                             0.0156                                                                            0   0  5   5  0   0  10  5  0                                             0.0039                                                                            0   0  5   0  0   0  5   5  0                                          12 0.25                                                                              50  100                                                                              95  90 85  90 100 100                                                                              30                                            0.0625                                                                            25  98 65  70 60  70 100 100                                                                              25                                            0.0156                                                                            20  80 50  45 40  45 98  75 23                                            0.0039                                                                            15  70 35  20 35  35 100 70 22                                         13 0.25                                                                              95  98 100 100                                                                              90  90 100 100                                                                              20                                            0.0625                                                                            65  90 98  95 75  75 100 98 15                                            0.0156                                                                            20  70 75  75 40  35 100 80 14                                            0.0039                                                                            25  40 55  30 30  30 90  55 8                                          14 0.25                                                                              60  45 40  65 50  60 90  75 13                                            0.0625                                                                            30  40 25  25 25  35 90  40 10                                            0.0156                                                                            5   15 10  10 20  25 30  25 8                                             0.0039                                                                            5   5  5   5  5   10 20  10 0                                          15 0.25                                                                              100 100                                                                              100 100                                                                              100 100                                                                              100 100                                                                              20                                            0.0625                                                                            95  80 75  85 80  75 100 80 15                                            0.0156                                                                            50  65 75  50 40  40 100 45 10                                            0.0039                                                                            20  20 20  30 20  25 70  30 5                                          16 0.25                                                                              5   50 25  0  0   0  30  0  0                                             0.0625                                                                            5   10 5   0  0   0  10  0  0                                             0.0156                                                                            5   5  5   0  0   0  15  0  0                                          17 0.25                                                                              15  90 95  20 20  30 98  20 15                                            0.0625                                                                            10  75 70  15 20  25 100 15 10                                            0.0156                                                                            5   45 50  10 15  15 50  10 5                                          18 0.25                                                                              20  35 65  20 20  25 60  15 7                                             0.0625                                                                            10  30 55  15 15  15 40  10 5                                             0.0156                                                                            5   25 40  5  15  10 20  5  0                                          19 0.25                                                                              20  50 60  20 20  25 55  15 10                                            0.0625                                                                            15  10 45  15 20  20 35  5  5                                             0.0156                                                                            10  5  35  15 15  10 30  10 5                                          20 0.25                                                                              35  98 95  25 45  40 100 25 22                                            0.0625                                                                            25  80 55  20 30  35 98  20 18                                            0.0156                                                                            15  40 50  15 20  25 35  10 12                                         21 0.25                                                                              10  30 65  25 20  25 50  20 5                                             0.0625                                                                            5   15 35  15 5   15 25  15 0                                             0.0156                                                                            5   10 20  15 5   5  5   5  0                                          22 0.25                                                                              5   40 45  20 10  15 40  10 0                                             0.0625                                                                            5   35 40  15 5   15 35  0  0                                             0.0156                                                                            0   20 25  10 5   5  20  10 0                                          23 0.25                                                                              15  75 50  15 20  25 75  10 11                                            0.0625                                                                            10  65 50  15 20  15 45  5  7                                             0.0156                                                                            5   30 25  10 10  5  25  5  0                                          24 0.25                                                                              25  90 65  20 25  25 95  25 20                                            0.0625                                                                            20  70 70  20 20  25 80  10 19                                            0.0156                                                                            5   35 55  15 15  20 75  5  7                                          25 0.25                                                                              40  90 65  65 35  50 95  40 16                                            0.0625                                                                            30  40 60  35 25  25 40  25 7                                             0.0156                                                                            15  15 50  25 10  15 15  0  5                                             0.0039                                                                            5   10 10  15 5   10 10  5  0                                          26 0.25                                                                              35  85 60  60 35  45 85  60 17                                            0.0625                                                                            25  55 55  30 25  40 50  25 10                                            0.0156                                                                            0   25 40  5  10  15 15  15 0                                             0.0039                                                                            0   0  5   5  0   0  10  5  0                                          27 0.25                                                                              30  65 90  75 25  40 100 80 13                                            0.0625                                                                            20  40 75  50 15  35 90  50 10                                            0.0156                                                                            10  25 35  35 5   25 70  30 8                                             0.0039                                                                            10  25 25  30 10  15 75  25 7                                          28 0.25                                                                              10  25 60  50 15  20 85  20 8                                             0.0625                                                                            5   15 20  45 5   10 75  20 5                                             0.0156                                                                            5   5  10  10 5   5  40  15 0                                             0.0039                                                                            5   10 10  15 5   5  50  10 3                                          29 0.25                                                                              70  95 100 95 75  70 100 100                                                                              12                                            0.0625                                                                            50  90 65  70 60  60 95  100                                                                              8                                             0.0156                                                                            15  70 40  25 35  45 85  60 7                                             0.0039                                                                            5   25 20  20 15  20 75  35 5                                          30 0.25                                                                              30  75 40  65 25  25 98  60 15                                            0.0625                                                                            15  40 30  40 20  20 70  40 16                                            0.0156                                                                            10  20 25  35 15  20 50  25 8                                             0.0039                                                                            10  20 25  20 15  20 40  15 6                                          31 0.25                                                                              20  95 70  75 35  55 100 75 20                                            0.0625                                                                            15  75 60  60 25  40 100 60 17                                            0.0156                                                                            10  60 40  20 20  30 70  20 16                                            0.0039                                                                            10  50 40  15 20  35 75  15 14                                         32 0.25                                                                              25  20 45  65 20  25 90  50 15                                            0.0625                                                                            15  15 35  25 15  20 80  25 10                                            0.0156                                                                            5   10 10  10 5   5  20  10 5                                             0.0039                                                                            5   15 10  10 5   10 40  5  5                                          33 0.25                                                                              5   10 10  15 5   5  15  5  5                                             0.0625                                                                            5   5  5   5  0   5  5   5  0                                             0.0156                                                                            0   10 5   5  0   5  5   0  0                                          41 0.25                                                                              20  98 100 90 20  30 100 40 15                                            0.0625                                                                            15  90 50  60 20  20 98  25 10                                         42 0.25                                                                              20  95 100 40 20  30 95  40 15                                            0.0625                                                                            15  65 90  30 15  20 75  15 5                                          43 0.25                                                                              10  65 30  20 15  10 100 25 10                                            0.0625                                                                            5   30 25  20 10  10 70  15 5                                          44 0.25                                                                              25  95 100 90 25  35 100 45 15                                            0.0625                                                                            15  60 50  35 20  20 90  25 15                                         45 0.25                                                                              98  100                                                                              100 100                                                                              80  95 100 50 17                                            0.0625                                                                            35  70 70  60 35  50 100 25 15                                         46 0.25                                                                              20  95 100 70 20  15 100 45 15                                            0.0625                                                                            10  60 65  45 20  5  80  25 10                                         47 0.25                                                                              20  95 90  70 30  20 95  65 15                                            0.0625                                                                            15  90 35  55 25  15 98  40 10                                         48 0.25                                                                              70  65 80  98 75  65 100 60 16                                            0.0625                                                                            25  35 30  80 35  35 90  15 10                                         49 0.25                                                                              20  10 35  60 20  20 80  20 10                                            0.0625                                                                            5   5  30  45 10  10 70  10 5                                          50 0.25                                                                              5   60 35  25 10  10 75  15 10                                            0.0625                                                                            5   15 35  15 10  10 50  10 10                                         51 0.25                                                                              45  75 40  80 55  45 98  20 12                                            0.0625                                                                            25  95 40  45 30  45 70  20 7                                          52 0.25                                                                              95  100                                                                              100 98 95  100                                                                              100 100                                                                              25                                            0.0625                                                                            65  95 95  95 80  90 100 98 15                                         53 0.25                                                                              25  90 95  80 40  45 95  98 16                                            0.0625                                                                            20  75 90  40 20  20 70  60 12                                         54 0.25                                                                              30  90 98  98 80  70 100 75 16                                            0.0625                                                                            25  90 100 70 45  75 90  25 15                                         55 0.25                                                                              20  70 75  65 30  20 95  15 10                                            0.0625                                                                            60  90 80  100                                                                              70  70 100 45 15                                         56 0.25                                                                              60  90 98  98 80  85 100 98 16                                            0.0625                                                                            35  90 85  75 40  55 90  70 15                                         57 0.25                                                                              15  55 40  40 25  15 100 15 8                                             0.0625                                                                            15  30 35  10 10  10 20  10 5                                          58 0.25                                                                              80  95 90  85 85  85 100 65 18                                            0.0625                                                                            40  90 65  80 50  40 100 50 15                                         __________________________________________________________________________

The herbicidal compositions of this invention, including concentrateswhich require dilution prior to application, may contain at least oneactive ingredient and an adjuvant in liquid or solid form. Thecompositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers, and conditioningagents to provide compositions in the form of finely-divided particulatesolids, granules, pellets, solutions, dispersions or emulsions. Thus, itis believed that the active ingredient could be used with an adjuvantsuch as a finely-divided solid, a liquid of organic origin, water, awetting agent, a dispersing agent, an emulsifying agent or any suitablecombination of these.

Suitable wetting agents are believed to include alkyl benzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides,long chain acid esters of sodium isothionate, esters of sodiumsulfosuccinate, sulfated or sulfonated fatty acid esters, petroleumsulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols,polyoxyethylene derivatives of alkylphenols (particularly isooctylphenoland nonylphenol) and polyoxyethylene derivatives of the mono-higherfatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferreddispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalenesulfonate, and polymethylene bisnaphthalene sulfonate. Wettable powdersare water-dispersible compositions containing one or more activeingredients, an inert solid extender and one or more wetting anddispersing agents. The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, attapulgite clay and synthetic magnesium silicate.The wettable powders compositions of this invention usually contain fromabove 0.5 to 60 parts (preferably from 5-20 parts) of active ingredient,from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent,from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant andfrom 5 to about 95 parts (preferably 5-50 parts) of inert solidextender, all parts being by weight of the total composition. Whererequired, from about 0.1 to 2.0 parts of the solid inert extender can bereplaced by a corrosion inhibitor or anti-foaming agent or both.

Other formulations include dust concentrates comprising from 0.1 to 60%by weight of the active ingredient on a suitable extender; these dustsmay be diluted for application at concentrations within the range offrom about 0.1-10% by weight.

Aqueous suspensions or emulsions may be prepared by stirring anonaqueous solution of a water-insoluble active ingredient and anemulsification agent with water until uniform and then homogenizing togive stable emulsion of very finely divided particles. The resultingconcentrated aqueous suspension is characterized by its extremely smallparticle size, so that when diluted and sprayed, coverage is veryuniform. Suitable concentrations of these formulations contain fromabout 0.1-60%, preferably 5-50% by weight of active ingredient, theupper limit being determined by the solubility limit of activeingredient in the solvent. Concentrates are usually solutions of activeingredient in water-immiscible or partially water-immiscible solventstogether with a surface active agent. Suitable solvents for the activeingredient of this invention include dimethylformamide,dimethylsulfoxide, N-methyl-pyrrolidone, hydrocarbons, andwater-immiscible ethers, esters, or ketones. However, other highstrength liquid concentrates may be formulated by dissolving the activeingredient in a solvent then diluting, e.g., with kerosene, to sprayconcentration.

The concentrate compositions herein generally contain from about 0.1 to95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50parts (preferably 1-25 parts) surface active agent and where requiredabout 5 to 94 parts solvent, all parts being be weight based on thetotal weight of emulsifiable oil.

Granules are physically stable particulate compositions comprisingactive ingredient adhering to or distributed through a basic matrix ofan inert, finely-divided particulate extender. In order to aid leachingof the active ingredient from the particulate extender, a surface activeagent can be present in the composition. Natural clays, pyrophyllites,illite, and vermiculite are examples of operable classes of particulatemineral extenders. The preferred extenders are the porous, absorptivepreformed particles such as preformed and screened particulateattapulgite or heat expanded, particulate vermiculite and thefinely-divided clays such as kaolin clays, hydrated attapulgite orbentonitic clays. These extenders are sprayed or blended with the activeingredient to form the herbicidal granules.

The granular compositions of this invention may contain from about 0.1to about 30 parts by weight of active ingredient per 100 parts by weightof clay and 0 to about 5 parts by weight of surface active agent per 100parts by weight of particulate clay.

The compositions of this invention can also contain other additaments,for example, fertilizers, other herbicides, other pesticides, safenersand the like used as adjuvants or in combination with any of theabove-described adjuvants. Chemicals useful in combination with theactive ingredients of this invention included, for example, triazines,ureas, sulfonylureas, carbamates, acetamides, acetanilides, uracils,acetic acid or phenol derivatives, thiol- carbamates, triazoles,azolopyrimidines, benzoic acid and its derivatives, nitriles, biphenylethers, nitrobenzenes and the like such as:

Heterocyclic Nitrogen/Sulfur Derivatives

2-Chloro-4-ethylamino-6-isopropylamino-s-triazine

2-Chloro-4,6-bis(isopropylamino)-s-triazine

2-Chloro-4,6-bis(ethylamino)-s-triazine

3-Isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide

3-Amino-1,2,4-triazole

6,7-Dihydrodipyrido(1,2-:2',1'-c)-pyrazidiinium salt

5-Bromo-3-isopropyl-6-methyluracil

1,1'-Dimethyl-4,4'-bypyridinium

2-(4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid

Isopropylamine salt of2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid

Methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate andmethyl 2-(4-isopropyl-4-methyl- 5-oxo-2-imidazolin-2-yl)-p-toluate

Ureas/Sulfonylureas

N-(4-Chlorophenoxy) phenyl-N,N-dimethylurea

N,N-dimethyl-N'-(3-chloro-4-methylphenyl) urea

3-(3,4-dichlorophenyl)-1,1-dimethylurea

1,3-Dimethyl-3-(2-benzothiazolyl) urea

3-(p-Chlorophenyl)-1,1-dimethylurea

1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea

2-Chloro-N[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide

N-(2-methoxycarbonylphenylsulfonyl()-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)urea

Methyl 2-(((((4,6-dimethyl-2-pyrimidinyl)amino)-carbonyl)amino)sulfonyl)benzoate

Ethyl 1-[methyl 2-(((((4,6-dimethyl-2-pyrimidinyl)-amino)carbonyl)amino)sulfonyl)] benzoate

Methyl-2((4,6-dimethoxy pyrimidin-2-yl) aminocarbonyl)amino sulfonylmethyl) benzoate

Methyl2-(((((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)carbonyl)amino)sulfonyl)benzoate

Carbamates/Thiolcarbamates

2-Chloroallyl diethyldithiocarbamate

S-(4-chlorobenzyl)N,N-diethylthiolcarbamate

Isopropyl N-(3-chlorophenyl) carbamate

S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate

S-N,N-dipropylthiolcarbamate

S-propyl N,N-dipropylthiolcarbamate

S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate

Acetamides/Acetanilides/Anilines/Amides

2-Chloro-N,N-diallylacetamide

N,N-dimethyl-2,2-diphenylacetamide

N-(2,4-dimethylthien-3-yl)-N-(1-methoxyprop-2-yl)-2-chloroacetamide

N-(1H-pyrazol-1-ylmethyl-N-(2,4-dimethylthien-3-yl)-2-chloroacetamide

N-(1-pyrazol-1-ylmethyl)-N-(4,6-dimethoxypyrimidin-5-yl)-2-chloroacetamide

N-(2,4-dimethyl-5-[[[(trifluoromethyl) sulfonyl]amino]-phenyl]acetamide

N-Isopropyl-2-chloroacetanilide

N-Isopropyl-1-(3,5,5-trimethylcyclohexen-1-yl)-2-chloroacetamide

2',6'-Diethyl-N-(butoxymethyl)-2-chloroacetanilide

2',6'-Diethyl-N-(2-n-propoxyethyl)-2-chloroacetanilide

2',6'-Dimethyl-N-(1-pyrazol-1-ylmethyl)-2-chloroacetanilide

2',6'-Diethyl-N-methoxymethyl-2-chloroacetanilide

2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide2'-Methyl-6'-ethyl-N-(ethoxymethyl)-2-chloro-acetanilide

α,α,α-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide

Acids/Esters/Alcohols

2,2-Dichloropropionic acid

2-Methyl-4-chlorophenoxyacetic acid

2,4-Dichlorophenoxyacetic acid

Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate

3-Amino-2,5-dichlorobenzoic acid

2-Methoxy-3,6-dichlorobenzoic acid

2,3,6-Trichlorophenylacetic acid

N-1-naphthylphthalamic acid

Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

4,6-Dinitro-o-sec-butylphenol

N-(phosphonomethyl)glycine and its salts

Butyl (R)-2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]-phenoxy]propanoate

Ethers

2,4-Dichlorophenol-4-nitrophenyl ether

2-Chloro-α,α,α-trifluoro-p-tolyl-3-ethoxy-4-nitro-diphenyl ether

5-(2'chloro-4-trifluoromethylphenoxy)-N-methylsulfonyl-2-nitrobenazmide

1'-(Carboethoxy) ethyl5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

Miscellaneous

2,6-Dichlorobenzonitrile

Monosodium acid methanearsonate

Disodium methanearsonate

2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone

7-Oxabicyclo (2.2.1) heptane,1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-, exo-

Glufosinate and salts thereof

Glyphosate and salts thereof.

Fertilizers useful in combination with the active ingredients include,for example, ammonium nitrate, urea, potash and superphosphate. Otheruseful additaments include materials in which plant organisms take rootand grow such as compost, manure, humus, sand and the like.

Herbicidal formulations of the types described above contemplated aswithin the purview of this invention are exemplified in illustrativeembodiments below.

    ______________________________________                                        I. Emulsifiable Concentrates                                                                     Weight Percent                                             ______________________________________                                        Compound No. 8       11.60                                                    Aromatic 200 (Exxon, Houston, Texas):                                                              78.40                                                    gamma butyrolactone (4:1)                                                     Armul 1496 (Stepan, Winder, GA)                                                                    5.00                                                     Armul 1505 (Stepan, Winder, GA                                                                     5.00                                                     ______________________________________                                    

    ______________________________________                                        II. Suspension Concentrate                                                                       g/l                                                        ______________________________________                                        Compound No. 8       206.4                                                    Propylene glycol     40.0                                                     Atlox 4913 (ICI, Wilmington, DE)                                                                   20.0                                                     Atlox 4896 (ICI, Wilmington, DE)                                                                   10.0                                                     Rhodorsil 432R (Rhone Poulenc,                                                                     1.0                                                      Paris, France)                                                                Rhodopol 23 (Rhone Poulenc,                                                                        2.0                                                      Paris, France)                                                                Phylatol (Coalite, Derbyshire,                                                                     2.0                                                      Great Britain)                                                                Water (De-mineralised)                                                                             805.5                                                    ______________________________________                                    

When operating in accordance with the present invention, effectiveamounts of the compounds of this invention are applied to the soilcontaining the seeds, or vegetative propagules or may be incorporatedinto the soil media in any convenient fashion. The application of liquidand particulate solid compositions to the soil can be carried out byconventional methods, e.g., power duster, boom and hand sprayers andspray dusters. The compositions can also be applied from airplanes as adust or a spray because of their effectiveness at low dosages. The exactamount of active ingredient to be employed is dependent upon variousfactors, including the plant species and stage of development thereof,the type and condition of soil, the amount of rainfall and the specificcompounds employed. In elective pre-emergence application or to thesoil, a dosage of from about 0.001 to about 11.2 kg/ha, preferably fromabout 0.01 to about 0.5 kg/ha, is usually employed. Lower or higherrates may be required in some instances. One skilled in the art canreadily determine from this specification, including the above examplesthe optimum rate to be applied in any particular case.

The term "soil" is employed in its broadest sense to be-inclusive of allconventional "soils" as defined in Webster's New InternationalDictionary, Second Edition, Unabridged (1961). Thus, the term refers toany substance or medium in which vegetation may take root and grow, andincludes not only earth but also compost, manure, muck, humus, loam,silt, mire, clay, sand and the like, adapted to support plant growth.

Although this invention has been described with respect to specificembodiments, the details of these embodiments are not to be construed aslimitations. Various equivalents, changes and modifications may be madewithout departing from the spirit and scope of this invention, and it isunderstood that such equivalent embodiments are part of this invention.

We claim:
 1. A compound according to Formula I: ##STR13## andagriculturally acceptable salts and hydrates thereof wherein R₁ isindependently C₁₋₈ alkyl; C₃₋₈ cycloalkyl, cycloalkenyl,cycloalkylalkyl, or cycloalkylalkyl; C₂₋₈ alkenyl or alkynyl; benzyl; orsaid R₁ members substituted with halogen, amino, nitro, cyano, hydroxy,C₁₋₈ alkoxy, C₁₋₈ alkylthio, --C(═X)YR₈, --C(═X)R₉, YR₁₀, or NR₁₁ R₁₂;R₂ is C₁₋₆ haloalkyl; R₃ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, CHO or CH₂ OH;R₄ members are independently an R₁ member, C₁₋₈ thioalkyl, C₁₋₈polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, C₆₋₂aryl, aralkyl or alkaryl, --C(X)YR₁₃, --C(X)R₁₄, YR₁₅, or NR₁₆ R₁₇group; or two R₄ groups may be combined through a saturated and/orunsaturated carbon, or --(C═X)--, linkage to form a cyclic ring havingup to 9 ring members which may be substituted with an R₁ member,halogen, amino, nitro, cyano, hydroxy, C₆₋₁₂ aryl, aralkyl, alkaryl,--C(═X)YR₁₃, --C(═X)R₁₄, YR₁₅ or NR₁₆ R₁₇ ; X is O, S(O)_(m), NR₁₉ orCR₂₀ R₂₁ ; Y is O, S(O)_(m) or NR₂₂ ; wherein at least one R₄ member isa non-halogen; R₈₋₂₂ are hydrogen, C₁₋₈ alkyl, C₃₋₈ cycloalkyl,cycloalkenyl, cycloalkylalkyl, or cycloalkylalkyl, C₂₋₈ alkenyl oralkynyl, benzyl, or said R₁ members substituted with halogen, amino,nitro, cyano, hydroxy, C₁₋₈ alkoxy, C₁₋₈ alkylthio, C₆₋₂ aryl, aralkyl,alkaryl, carboxyl, alkoxy C₁₋₈ -alkyl, C₁₋₈ alkylamino, di-C₁₋₈-alkylamino, C₁₋₈ alkoxy, or carbamyl; m is 0-2 and n is 1-5.
 2. Acompounds according to claim 1 having formula ##STR14## andagriculturally-acceptable salts and hydrates thereof wherein R₁ is C₁₋₆alkyl;R₂ is C₁₋₆ haloalkyl; R₃ is C₁₋ ₆ alkyl, C₁₋₆ haloalkyl, CHO orCH₂ OH; R₅ and R₆ are independently halogen; and R₇ is an R₁ member,##STR15## YR₁₀, or NR₁₁ R₁₂.
 3. A compound, salt and hydrate accordingto claim 2 whereinR₁ is CH₃ ; R₂ is CF₃ ; R₃ is CH₃, CH₂ F or CF₂ H; R₅is F; R₆ is Cl; and R₇ is ##STR16##
 4. A compound according to claim 3wherein said compounds are selected from the group consistingof2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester;2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid ethyl ester;2-chloro-5-[4-difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester; and2-chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester.
 5. Herbicidal composition comprising anadjuvant and a herbicidally-effective amount of a compound according toFormula I: ##STR17## and agriculturally acceptable salts and hydratesthereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈ cycloalkyl,cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈ alkenyl oralkynyl; benzyl; or said R₁ members substituted with halogen, amino,nitro, cyano, hydroxy, C₁₋₈ alkoxy, C₁₋₈ alkylthio, --C(═X)YR₈,--C(═X)R₉, YR₁₀, or NR₁₁ R₁₂ ;R₁₂ is C₁₋₆ haloalkyl; R₃ is C₁₋₆ alkyl,C₁₋₆ haloalkyl, CHO or CH₂ OH; R₄ members are independently an R₁member, C₁₋₈ thioalkyl, C₁₋₈ polyalkoxyalkyl, carbamyl, halogen, amino,nitro, cyano, hydroxy, C₆ ₂₋₁₂ aryl, aralkyl or alkaryl, --C(X)YR₁₃,--C(X)R₁₄, YR₁₅, or NR₁₆ R₁₇ group; or two R₄ groups may be combinedthrough a saturated and/or unsaturated carbon, or --(C═X)--, linkage toform a cyclic ring having up to 9 ring members which may be substitutedwith an R₁ member, halogen, amino, nitro, cyano, hydroxy, C₆₋₁₂ aryl,aralkyl, alkaryl, --C(═X)YR₁₃, --C(═X)R₁₄, YR₁₅ or NR₁₆ R₁₇ ; X is O,S(O)_(m), NR₁₉ or CR₂₀ R₂₁ ; Y is O, S(O)_(m) or NR₂₂ ; wherein at leastone R₄ member is a non-halogen: R₈₋₂₂ are hydrogen, C₁₋₈ alkyl, C₃₋₈cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl, C₂₋₈alkenyl or alkynyl, benzyl, or said R₁ members substituted with halogen,amino, nitro, cyano, hydroxy, C₁₋₈ alkoxy, C₁₋₈ alkylthio, C₆₋₁₂ aryl,aralkyl, alkaryl, carboxyl, alkoxy-C₁₋₈ -alkyl, C₁₋₈ alkylamino, di-C₁₋₈-alkylamino, C₁₋₈ alkoxy, or carbamyl; m is 0-2 and n is 1-5. 6.Compositions according to claim 5 wherein the compound of Formula I isas in formula II: ##STR18## and agriculturally-acceptable salts andhydrates thereof wherein R₁ is C₁₋₆ alkyl;R₂ is C₁₋₆ haloalkyl; R₃ isC₁₋₆ alkyl, C₁₋₆ haloalkyl, CHO or CH₂ OH; R₅ and R₆ are independentlyhalogen; and R₇ is an R₁ member, ##STR19## YR₁₀, or NR₁₁ R₁₂. 7.Composition according to claim 6 where in Formula IIR₁ is CH₃ ; R₂ isCF₃ ; R₃ is CH₃, CH₂ F or CF₂ H; R₅ is F; R₆ is Cl; and R₇ is ##STR20##8. Composition according to claim 7 wherein said compounds is selectedfrom the group consistingof2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoic acid, 1-methylethyl ester;2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid ethyl ester;2-chloro-5-[4-difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester; and 2-chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoic acid,1-methylethyl ester.
 9. Method for combatting undesirable plants incrops comprising applying to the locus thereof a herbicidally-effectiveamount of a compound according to Formula I: ##STR21## andagriculturally acceptable salts and hydrates thereof wherein R₁ isindependently C₁₋₈ alkyl; C₃₋₈ cycloalkyl, cycloalkenyl,cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈ alkenyl or alkynyl; benzyl;or said R₁ members substituted with halogen, amino, nitro, cyano,hydroxy, C₁₋₈ alkoxy, C₁₋₈ alkylthio, --C(═X)YR₈, --C(═X)R₉, YR₁₀, orNR₁₁ R₁₂ ;R₂ is C₁₋₆ haloalkyl; R₃ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, CHO orCH₂ OH; R₄ members are independently an R₁ member, C₁₋₈ thioalkyl, C₁₋₈polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, C₆₋₁₂aryl, aralkyl or alkaryl, --C(X)YR₁₃, --C(X)R₁₄, YR₁₅, or NR₁₆ R₁₇group; or two R₄ groups may be combined through a saturated and/orunsaturated carbon, or --(C═X)--, linkage to form a cyclic ring havingup to 9 ring members which may be substituted with an R₁ member,halogen, amino, nitro, cyano, hydroxy, C₆₋₁₂ aryl, aralkyl, alkaryl,--C(═X)YR₁₃, --C(═X)R₁₄, YR₁₅ or NR₁₆ R₁₇ ; X is O, S(O)_(m), NR₁₉ orCR₂₀ R₂₁ ; Y is O, S(O)_(m) or NR₂₂ ; wherein at least one R₄ member isa non-halogen; R₈₋₂₂ are hydrogen, C₁₋₈ alkyl, C₃₋₈ cycloalkyl,cycloalkenyl, cycloalkylalkyl, or cycloalkenyl alkyl, C₂₋₈ alkenyl oralkynyl, benzyl, or said R₁ members substituted with halogen, amino,nitro, cyano, hydroxy, C₁₋₈ alkoxy, C₁₋₈ alkylthio, C₆₋₁₂ aryl, aralkyl,alkaryl, carboxyl, alkoxy-C₁₋₈ -alkyl, C₁₋₈ alkylamino, di-C₁₋₈-alkylamino, C₁₋₈ alkoxy, or carbamyl; m is 0-2 and n is 1-5.
 10. Methodaccording to claim 9 wherein the compounds of Formula I is compoundsaccording to Formula II: ##STR22## and agriculturally-acceptable saltsand hydrates thereof wherein R₁ is C₁₋₆ alkyl;R₂ is C₁₋₆ haloalkyl; R₃is C₁₋₆ alkyl, C₁₋₆ haloalkyl, CHO or CH₂ OH; R₅ and R₆ areindependently halogen; and R₇ is an R₁ member, ##STR23## YR₁₀, or NR₁₁R₁₂.
 11. Method according to claim 10 wherein in the compound, salt andhydrate of Formula II.R₁ is CH₃ ; R₂ is CF₃ ; R₃ is CH₃, CH₂ F or CF₂ H;R₅ is F; R₆ is Cl; and R₇ is ##STR24##
 12. Method according to claim 11wherein said compound is selected from the group consistingof2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl 5 ester;2-chloro-5-[1,4-dimethyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid ethyl ester;2-chloro-5-[4-difluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3yl]-4-fluorobenzoicacid, 1-methylethyl ester; and2-chloro-4-fluoro-5-[4-(fluoromethyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzoicacid, 1-methylethyl ester.